Germanium- and zirconium-containing compositions for vapor deposition of zirconium-containing films

ABSTRACT

Disclosed are Germanium- and Zirconium-containing precursors having one of the following formulae: 
     
       
         
         
             
             
         
       
     
     wherein each R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9  and R 10  is independently selected from H; a C1-C5 linear, branched, or cyclic alkyl group; and a C1-C5 linear, branched, or cyclic fluoroalkyl groups. Also disclosed are methods of synthesizing the disclosed precursors and using the same to deposit Zirconium-containing films on substrates via vapor deposition processes.

TECHNICAL FIELD

Disclosed are Germanium- and Zirconium-containing precursors. Alsodisclosed are methods of synthesizing the disclosed precursors and usingthe same to deposit Zirconium-containing films on substrates via vapordeposition processes.

BACKGROUND

With the scaling down of semiconductor devices such as dynamic randomaccess memory (DRAM), new materials with high dielectric constant arerequired. Indeed, in order to store a sufficient charge in a capacitorwith a smaller surface area, capacitors with higher permittivity areneeded. Among high-k dielectrics, Group 4 based materials, such as HfO₂or ZrO₂, are very promising since their dielectric constant is higherthan SiO₂ or Al₂O₃. However, their dielectric constant varies dependingon their crystalline form (Thin Solid Films 486 (2005) 125-128).

Thick ZrO₂ layers tend to have a unstable crystalline phase and to havehigher leakage current (Applied Physics Reviews (2012) version14-9-2012). To prevent these defects, a thin layer of Al₂O₃ has beenintroduced in between two layers of ZrO₂, forming a so-called ZAZcapacitor, stabilizing the crystalline phase and reducing the leakagecurrent (Applied Physics Letters 93, 033511 (2008); J. Vac. Sci. Techno.A 4 (6), 1986; Microelectronic Engineering 86 (2009) 1789-1795).

The cubic/tetragonal crystalline phase of the ZrO₂ layer, which is thephase having the highest k-value, has also been stabilized by dopingZrO₂ with a small amount of silicon or germanium (US2013/0208403A1 forsilicon and Journal of Applied Physics, 2009, 106, 024107;Microelectronic Engineering, 2009, 86, 1626; Applied Physics Letters,2011, 99, 121909 for germanium).

Group 4 alkylamide precursors containing cyclopentadienyl ligands havebeen developed, such as the one show below (Dussarrat et al.,WO2007/141059; Niinisto et al., Journal of Materials Chemistry (2008),18(43), 5243-5247). These precursors show a higher thermal stability incomparison to tetrakis alkylamide precursors.

Similar to these compounds, a few germylcyclopentadienyl Group 4compounds have been reported such as (trimethylgermyl)cyclopentadienyltris(dimethylamino) Titanium(IV) (Journal of Organometallic Chemistry,1975, 101, 295).

A need remains for developing novel, liquid or low melting point (<50°C.), highly thermally stable, with low viscosity, zirconium precursormolecules suitable for vapor phase thin film deposition with controlledthickness and composition at high temperature.

SUMMARY

Disclosed are Germanium- and Zirconium-film forming compositionscomprising a Germanium- and Zirconium-containing precursor having thefollowing formula:

wherein each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹ and R¹⁰ is independentlyselected from H; a C1-C5 linear, branched, or cyclic alkyl group; or aC1-C5 linear, branched, or cyclic fluoroalkyl group. R¹, R² and R³ maybe identical or different. R⁴, R⁵, R⁶ and R⁷ may be identical ordifferent. R⁸ and R⁹ may be identical or different. The disclosedGermanium- and Zirconium-film forming compositions may further includeone or more of the following aspects:

-   -   Each R¹ and R² and R³ being independently selected from H, F,        CF₃, Me, Et, nPr, iPr, nBu, iBu, sBu or tBu;    -   Each R⁴, R⁵, R⁶ and R⁷ being independently selected from H, F,        CF₃, Me, Et, nPr, iPr, nBu, iBu, sBu or tBu;    -   Each R⁸ and R⁹ being independently selected from H, Me, Et, nPr,        iPr, nBu, iBu, sBu or tBu;    -   Each R¹⁰ being Me, Et, nPr, iPr, nBu, iBu, sBu, or tBu;    -   the Germanium- and Zirconium-containing precursor being        (trimethylgermyl)cyclopentadienyl tris(Dimethylamino)        Zirconium(IV) (Zr(TMG-Cp)(NMe₂)₃);    -   the Germanium- and Zirconium-containing precursor being        (trimethylgermyl)cyclopentadienyl tris(methylamino)        Zirconium(IV) (Zr(TMG-Cp)(NHMe)₃);    -   the Germanium- and Zirconium-containing precursor being        (trimethylgermyl)cyclopentadienyl tris(Diethylamino)        Zirconium(IV) (Zr(TMG-Cp)(NEt₂)₃);    -   the Germanium- and Zirconium-containing precursor being        (trimethylgermyl)cyclopentadienyl tris(ethylamino) Zirconium(IV)        (Zr(TMG-Cp)(NHEt)₃);    -   the Germanium- and Zirconium-containing precursor being        (trimethylgermyl)cyclopentadienyl tris(ethylmethylamino)        Zirconium(IV) (Zr(TMG-Cp)(NEtMe)₃);    -   the Germanium- and Zirconium-containing precursor being        (trimethylgermyl)cyclopentadienyl tris(Di n-propylamino)        Zirconium(IV) (Zr(TMG-Cp)(NnPr₂)₃);    -   the Germanium- and Zirconium-containing precursor being        (trimethylgermyl)cyclopentadienyl tris(n-propylamino)        Zirconium(IV) (Zr(TMG-Cp)(NHnPr)₃);    -   the Germanium- and Zirconium-containing precursor being        (trimethylgermyl)cyclopentadienyl tris(Diisopropylamino)        Zirconium(IV) (Zr(TMG-Cp)(NiPr₂)₃);    -   the Germanium- and Zirconium-containing precursor being        (trimethylgermyl)cyclopentadienyl tris(isopropylamino)        Zirconium(IV) (Zr(TMG-Cp)(NHiPr)₃);    -   the Germanium- and Zirconium-containing precursor being        (trimethylgermyl)cyclopentadienyl tris(Di n-butylamino)        Zirconium(IV) (Zr(TMG-Cp)(NnBu₂)₃);    -   the Germanium- and Zirconium-containing precursor being        (trimethylgermyl)cyclopentadienyl tris(n-butylamino)        Zirconium(IV) (Zr(TMG-Cp)(NHnBu)₃);    -   the Germanium- and Zirconium-containing precursor being        (trimethylgermyl)cyclopentadienyl tris(Di isobutylamino)        Zirconium(IV) (Zr(TMG-Cp)(NiBu₂)₃);    -   the Germanium- and Zirconium-containing precursor being        (trimethylgermyl)cyclopentadienyl tris(isobutylamino)        Zirconium(IV) (Zr(TMG-Cp)(NHiBu)₃);    -   the Germanium- and Zirconium-containing precursor being        (trimethylgermyl)cyclopentadienyl tris(Di sec-butylamino)        Zirconium(IV) (Zr(TMG-Cp)(NsBu₂)₃);    -   the Germanium- and Zirconium-containing precursor being        (trimethylgermyl)cyclopentadienyl tris(sec-butylamino)        Zirconium(IV) (Zr(TMG-Cp)(NHsBu)₃);    -   the Germanium- and Zirconium-containing precursor being        (trimethylgermyl)cyclopentadienyl tris(Di tert-butylamino)        Zirconium(IV) (Zr(TMG-Cp)(NtBu₂)₃);    -   the Germanium- and Zirconium-containing precursor being        (trimethylgermyl)cyclopentadienyl tris(tert-butylamino)        Zirconium(IV) (Zr(TMG-Cp)(NHtBu)₃);    -   the Germanium- and Zirconium-containing precursor being        (trimethylgermyl)cyclopentadienyl tris(methoxy)Zirconium(IV)        (Zr(TMG-Cp)(OMe)₃);    -   the Germanium- and Zirconium-containing precursor being        (trimethylgermyl)cyclopentadienyl tris(ethoxy)Zirconium(IV)        (Zr(TMG-Cp)(OEt)₃);    -   the Germanium- and Zirconium-containing precursor being        (trimethylgermyl)cyclopentadienyl tris(n-propoxy)Zirconium(IV)        (Zr(TMG-Cp)(OnPr)₃);    -   the Germanium- and Zirconium-containing precursor being        (trimethylgermyl)cyclopentadienyl tris(iso-propoxy)        Zirconium(IV) (Zr(TMG-Cp)(OiPr)₃);    -   the Germanium- and Zirconium-containing precursor being        (trimethylgermyl)cyclopentadienyl tris(tert-butoxy)        Zirconium(IV) (Zr(TMG-Cp)(OtBu)₃);    -   the Germanium- and Zirconium-containing precursor being        (trimethylgermyl)cyclopentadienyl tris(sec-butoxy) Zirconium(IV)        (Zr(TMG-Cp)(OsBu)₃);    -   the Germanium- and Zirconium-containing precursor being        (trimethylgermyl)cyclopentadienyl tris(n-butoxy)Zirconium(IV)        (Zr(TMG-Cp)(OnBu)₃);    -   the Germanium- and Zirconium-containing precursor being        (trimethylgermyl)cyclopentadienyl tris(iso-butoxy) Zirconium(IV)        (Zr(TMG-Cp)(OiBu)₃);    -   the Germanium- and Zirconium-containing precursor being        (dimethylgermyl)cyclopentadienyl tris(Dimethylamino)        Zirconium(IV) (Zr(DMG-Cp)(NMe₂)₃);    -   the Germanium- and Zirconium-containing precursor being        (dimethylgermyl)cyclopentadienyl tris(methylamino) Zirconium(IV)        (Zr(DMG-Cp)(NHMe)₃);    -   the Germanium- and Zirconium-containing precursor being        (dimethylgermyl)cyclopentadienyl tris(Diethylamino)        Zirconium(IV) (Zr(DMG-Cp)(NEt₂)₃);    -   the Germanium- and Zirconium-containing precursor being        (dimethylgermyl)cyclopentadienyl tris(ethylamino) Zirconium(IV)        (Zr(DMG-Cp)(NHEt)₃);    -   the Germanium- and Zirconium-containing precursor being        (dimethylgermyl)cyclopentadienyl tris(ethylmethylamino)        Zirconium(IV) (Zr(DMG-Cp)(NEtMe)₃);    -   the Germanium- and Zirconium-containing precursor being        (dimethylgermyl)cyclopentadienyl tris(Di n-propylamino)        Zirconium(IV) (Zr(DMG-Cp)(NnPr₂)₃);    -   the Germanium- and Zirconium-containing precursor being        (dimethylgermyl)cyclopentadienyl tris(n-propylamino)        Zirconium(IV) (Zr(DMG-Cp)(NHnPr)₃);    -   the Germanium- and Zirconium-containing precursor being        (dimethylgermyl)cyclopentadienyl tris(Diisopropylamino)        Zirconium(IV) (Zr(DMG-Cp)(NiPr₂)₃);    -   the Germanium- and Zirconium-containing precursor being        (dimethylgermyl)cyclopentadienyl tris(isopropylamino)        Zirconium(IV) (Zr(DMG-Cp)(NHiPr)₃);    -   the Germanium- and Zirconium-containing precursor being        (dimethylgermyl)cyclopentadienyl tris(Di n-butylamino)        Zirconium(IV) (Zr(DMG-Cp)(NnBu₂)₃);    -   the Germanium- and Zirconium-containing precursor being        (dimethylgermyl)cyclopentadienyl tris(n-butylamino)        Zirconium(IV) (Zr(DMG-Cp)(NHnBu)₃);    -   the Germanium- and Zirconium-containing precursor being        (dimethylgermyl)cyclopentadienyl tris(Di isobutylamino)        Zirconium(IV) (Zr(DMG-Cp)(NiBu₂)₃);    -   the Germanium- and Zirconium-containing precursor being        (dimethylgermyl)cyclopentadienyl tris(isobutylamino)        Zirconium(IV) (Zr(DMG-Cp)(NHiBu)₃);    -   the Germanium- and Zirconium-containing precursor being        (dimethylgermyl)cyclopentadienyl tris(Di sec-butylamino)        Zirconium(IV) (Zr(DMG-Cp)(NsBu₂)₃);    -   the Germanium- and Zirconium-containing precursor being        (dimethylgermyl)cyclopentadienyl tris(sec-butylamino)        Zirconium(IV) (Zr(DMG-Cp)(NHsBu)₃);    -   the Germanium- and Zirconium-containing precursor being        (dimethylgermyl)cyclopentadienyl tris(Di tert-butylamino)        Zirconium(IV) (Zr(DMG-Cp)(NtBu₂)₃);    -   the Germanium- and Zirconium-containing precursor being        (dimethylgermyl)cyclopentadienyl tris(tert-butylamino)        Zirconium(IV) (Zr(DMG-Cp)(NHtBu)₃);    -   the Germanium- and Zirconium-containing precursor being        (dimethylgermyl)cyclopentadienyl tris(methoxy)Zirconium(IV)        (Zr(DMG-Cp)(OMe)₃);    -   the Germanium- and Zirconium-containing precursor being        (dimethylgermyl)cyclopentadienyl tris(ethoxy)Zirconium(IV)        (Zr(DMG-Cp)(OEt)₃);    -   the Germanium- and Zirconium-containing precursor being        (dimethylgermyl)cyclopentadienyl tris(n-propoxy)Zirconium(IV)        (Zr(DMG-Cp)(OnPr)₃);    -   the Germanium- and Zirconium-containing precursor being        (dimethylgermyl)cyclopentadienyl tris(isopropoxy) Zirconium(IV)        (Zr(DMG-Cp)(OiPr)₃);    -   the Germanium- and Zirconium-containing precursor being        (dimethylgermyl)cyclopentadienyl tris(tert-butoxy) Zirconium(IV)        (Zr(DMG-Cp)(OtBu)₃);    -   the Germanium- and Zirconium-containing precursor being        (dimethylgermyl)cyclopentadienyl tris(sec-butoxy) Zirconium(IV)        (Zr(DMG-Cp)(OsBu)₃);    -   the Germanium- and Zirconium-containing precursor being        (dimethylgermyl)cyclopentadienyl tris(n-butoxy)Zirconium(IV)        (Zr(DMG-Cp)(OnBu)₃);    -   the Germanium- and Zirconium-containing precursor being        (dimethylgermyl)cyclopentadienyl tris(isobutoxy)Zirconium(IV)        (Zr(DMG-Cp)(OiBu)₃);    -   the Germanium- and Zirconium-containing precursor being        (trifluorogermyl)cyclopentadienyl tris(Dimethylamino)        Zirconium(IV) (Zr(F₃Ge-Cp)(NMe₂)₃);    -   the Germanium- and Zirconium-containing precursor being        (trifluorogermyl)cyclopentadienyl tris(methylamino)        Zirconium(IV) (Zr(F₃Ge-Cp)(NHMe)₃);    -   the Germanium- and Zirconium-containing precursor being        (trifluorogermyl)cyclopentadienyl tris(Diethylamino)        Zirconium(IV) (Zr(F₃Ge-Cp)(NEt₂)₃);    -   the Germanium- and Zirconium-containing precursor being        (trifluorogermyl)cyclopentadienyl tris(ethylamino)Zirconium(IV)        (Zr(F₃Ge-Cp)(NHEt)₃);    -   the Germanium- and Zirconium-containing precursor being        (trifluorogermyl)cyclopentadienyl tris(Ethylmethylamino)        Zirconium(IV) (Zr(F₃Ge-Cp)(NEtMe)₃);    -   the Germanium- and Zirconium-containing precursor being        (trifluorogermyl)cyclopentadienyl tris(Di n-propylamino)        Zirconium(IV) (Zr(F₃Ge-Cp)(NnPr₂)₃);    -   the Germanium- and Zirconium-containing precursor being        (trifluorogermyl)cyclopentadienyl tris(n-propylamino)        Zirconium(IV) (Zr(F₃Ge-Cp)(NHnPr)₃);    -   the Germanium- and Zirconium-containing precursor being        (trifluorogermyl)cyclopentadienyl tris(Diisopropylamino)        Zirconium(IV) (Zr(F₃Ge-Cp)(NiPr₂)₃);    -   the Germanium- and Zirconium-containing precursor being        (trifluorogermyl)cyclopentadienyl tris(isopropylamino)        Zirconium(IV) (Zr(F₃Ge-Cp)(NHiPr)₃);    -   the Germanium- and Zirconium-containing precursor being        (trifluorogermyl)cyclopentadienyl tris(Di n-butylamino)        Zirconium(IV) (Zr(F₃Ge-Cp)(NnBu₂)₃);    -   the Germanium- and Zirconium-containing precursor being        (trifluorogermyl)cyclopentadienyl tris(n-butylamino)        Zirconium(IV) (Zr(F₃Ge-Cp)(NHnBu)₃);    -   the Germanium- and Zirconium-containing precursor being        (trifluorogermyl)cyclopentadienyl tris(Di isobutylamino)        Zirconium(IV) (Zr(F₃Ge-Cp)(NiBu₂)₃);    -   the Germanium- and Zirconium-containing precursor being        (trifluorogermyl)cyclopentadienyl tris(isobutylamino)        Zirconium(IV) (Zr(F₃Ge-Cp)(NHiBu)₃);    -   the Germanium- and Zirconium-containing precursor being        (trifluorogermyl)cyclopentadienyl tris(Di sec-butylamino)        Zirconium(IV) (Zr(F₃Ge-Cp)(NsBu₂)₃);    -   the Germanium- and Zirconium-containing precursor being        (trifluorogermyl)cyclopentadienyl tris(sec-butylamino)        Zirconium(IV) (Zr(F₃Ge-Cp)(NHsBu)₃);    -   the Germanium- and Zirconium-containing precursor being        (trifluorogermyl)cyclopentadienyl tris(Di tert-butylamino)        Zirconium(IV) (Zr(F₃Ge-Cp)(NtBu₂)₃);    -   the Germanium- and Zirconium-containing precursor being        (trifluorogermyl)cyclopentadienyl tris(tert-butylamino)        Zirconium(IV) (Zr(F₃Ge-Cp)(NHtBu)₃);    -   the Germanium- and Zirconium-containing precursor being        (trifluorogermyl)cyclopentadienyl tris(methoxy)Zirconium(IV)        (Zr(F₃Ge-Cp)(OMe)₃);    -   the Germanium- and Zirconium-containing precursor being        (trifluorogermyl)cyclopentadienyl tris(ethoxy)Zirconium(IV)        (Zr(F₃Ge-Cp)(OEt)₃);    -   the Germanium- and Zirconium-containing precursor being        (trifluorogermyl)cyclopentadienyl tris(n-propoxy)Zirconium(IV)        (Zr(F₃Ge-Cp)(OnPr)₃);    -   the Germanium- and Zirconium-containing precursor being        (trifluorogermyl)cyclopentadienyl tris(isopropoxy)Zirconium(IV)        (Zr(F₃Ge-Cp)(OiPr)₃);    -   the Germanium- and Zirconium-containing precursor being        (trifluorogermyl)cyclopentadienyl tris(tert-butoxy)Zirconium(IV)        (Zr(F₃Ge-Cp)(OtBu)₃);    -   the Germanium- and Zirconium-containing precursor being        (trifluorogermyl)cyclopentadienyl tris(sec-butoxy)Zirconium(IV)        (Zr(F₃Ge-Cp)(OsBu)₃);    -   the Germanium- and Zirconium-containing precursor being        (trifluorogermyl)cyclopentadienyl tris(n-butoxy)Zirconium(IV)        (Zr(F₃Ge-Cp)(OnBu)₃);    -   the Germanium- and Zirconium-containing precursor being        (trifluorogermyl)cyclopentadienyl tris(isobutoxy)Zirconium(IV)        (Zr(F₃Ge-Cp)(OiBu)₃);    -   the Germanium- and Zirconium-containing precursor being        (difluorogermyl)cyclopentadienyl tris(Dimethylamino)        Zirconium(IV) (Zr(F₂HGe-Cp)(NMe₂)₃);    -   the Germanium- and Zirconium-containing precursor being        (difluorogermyl)cyclopentadienyl tris(methylamino) Zirconium(IV)        (Zr(F₂HGe-Cp)(NHMe)₃);    -   the Germanium- and Zirconium-containing precursor being        (difluorogermyl)cyclopentadienyl tris(Diethylamino)        Zirconium(IV) (Zr(F₂HGe-Cp)(NEt₂)₃);    -   the Germanium- and Zirconium-containing precursor being        (difluorogermyl)cyclopentadienyl tris(ethylamino)Zirconium(IV)        (Zr(F₂HGe-Cp)(NHEO₃);    -   the Germanium- and Zirconium-containing precursor being        (difluorogermyl)cyclopentadienyl tris(Ethylmethylamino)        Zirconium(IV) (Zr(F₂HGe-Cp)(NEtMe)₃);    -   the Germanium- and Zirconium-containing precursor being        (difluorogermyl)cyclopentadienyl tris(Di n-propylamino)        Zirconium(IV) (Zr(F₂HGe-Cp)(NnPr₂)₃);    -   the Germanium- and Zirconium-containing precursor being        (difluorogermyl)cyclopentadienyl tris(n-propylamino)        Zirconium(IV) (Zr(F₂HGe-Cp)(NHnPr)₃);    -   the Germanium- and Zirconium-containing precursor being        (difluorogermyl)cyclopentadienyl tris(Diisopropylamino)        Zirconium(IV) (Zr(F₂HGe-Cp)(NiPr₂)₃);    -   the Germanium- and Zirconium-containing precursor being        (difluorogermyl)cyclopentadienyl tris(isopropylamino)        Zirconium(IV) (Zr(F₂HGe-Cp)(NHiPr)₃);    -   the Germanium- and Zirconium-containing precursor being        (difluorogermyl)cyclopentadienyl tris(Di n-butylamino)        Zirconium(IV) (Zr(F₂HGe-Cp)(NnBu₂)₃);    -   the Germanium- and Zirconium-containing precursor being        (difluorogermyl)cyclopentadienyl tris(n-butylamino)        Zirconium(IV) (Zr(F₂HGe-Cp)(NHnBu)₃);    -   the Germanium- and Zirconium-containing precursor being        (difluorogermyl)cyclopentadienyl tris(Di isobutylamino)        Zirconium(IV) (Zr(F₂HGe-Cp)(NiBu₂)₃);    -   the Germanium- and Zirconium-containing precursor being        (difluorogermyl)cyclopentadienyl tris(isobutylamino)        Zirconium(IV) (Zr(F₂HGe-Cp)(NHiBu)₃);    -   the Germanium- and Zirconium-containing precursor being        (difluorogermyl)cyclopentadienyl tris(Di sec-butylamino)        Zirconium(IV) (Zr(F₂HGe-Cp)(NsBu₂)₃);    -   the Germanium- and Zirconium-containing precursor being        (difluorogermyl)cyclopentadienyl tris(sec-butylamino)        Zirconium(IV) (Zr(F₂HGe-Cp)(NHsBO₃);    -   the Germanium- and Zirconium-containing precursor being        (difluorogermyl)cyclopentadienyl tris(Di tert-butylamino)        Zirconium(IV) (Zr(F₂HGe-Cp)(NtBu₂)₃);    -   the Germanium- and Zirconium-containing precursor being        (difluorogermyl)cyclopentadienyl tris(tert-butylamino)        Zirconium(IV) (Zr(F₂HGe-Cp)(NHtBu)₃);    -   the Germanium- and Zirconium-containing precursor being        (difluorogermyl)cyclopentadienyl tris(methoxy)Zirconium(IV)        (Zr(F₂HGe-Cp)(OMe)₃);    -   the Germanium- and Zirconium-containing precursor being        (difluorogermyl)cyclopentadienyl tris(ethoxy)Zirconium(IV)        (Zr(F₂HGe-Cp)(OEt)₃);    -   the Germanium- and Zirconium-containing precursor being        (difluorogermyl)cyclopentadienyl tris(n-propoxy)Zirconium(IV)        (Zr(F₂HGe-Cp)(OnPr)₃);    -   the Germanium- and Zirconium-containing precursor being        (difluorogermyl)cyclopentadienyl tris(isopropoxy)Zirconium(IV)        (Zr(F₂HGe-Cp)(OiPr)₃);    -   the Germanium- and Zirconium-containing precursor being        (difluorogermyl)cyclopentadienyl tris(tert-butoxy)Zirconium(IV)        (Zr(F₂HGe-Cp)(OtBu)₃);    -   the Germanium- and Zirconium-containing precursor being        (difluorogermyl)cyclopentadienyl tris(sec-butoxy)Zirconium(IV)        (Zr(F₂HGe-Cp)(OsBu)₃);    -   the Germanium- and Zirconium-containing precursor being        (difluorogermyl)cyclopentadienyl tris(n-butoxy)Zirconium(IV)        (Zr(F₂HGe-Cp)(OnBu)₃);    -   the Germanium- and Zirconium-containing precursor being        (difluorogermyl)cyclopentadienyl tris(isobutoxy)Zirconium(IV)        (Zr(F₂HGe-Cp)(OiBu)₃);    -   the Germanium- and Zirconium-containing precursor being        (monofluorogermyl)cyclopentadienyl tris(Dimethylamino)        Zirconium(IV) (Zr(FH₂Ge-Cp)(NMe₂)₃);    -   the Germanium- and Zirconium-containing precursor being        (monofluorogermyl)cyclopentadienyl tris(methylamino)        Zirconium(IV) (Zr(FH₂Ge-Cp)(NHMe)₃);    -   the Germanium- and Zirconium-containing precursor being        (monofluorogermyl)cyclopentadienyl tris(Diethylamino)        Zirconium(IV) (Zr(FH₂Ge-Cp)(NEt₂)₃);    -   the Germanium- and Zirconium-containing precursor being        (monofluorogermyl)cyclopentadienyl tris(ethylamino)        Zirconium(IV) (Zr(FH₂Ge-Cp)(NHEt)₃);    -   the Germanium- and Zirconium-containing precursor being        (monofluorogermyl)cyclopentadienyl tris(Ethylmethylamino)        Zirconium(IV) (Zr(FH₂Ge-Cp)(NEtMe)₃);    -   the Germanium- and Zirconium-containing precursor being        (monofluorogermyl)cyclopentadienyl tris(Di n-propylamino)        Zirconium(IV) (Zr(FH₂Ge-Cp)(NnPr₂)₃);    -   the Germanium- and Zirconium-containing precursor being        (monofluorogermyl)cyclopentadienyl tris(n-propylamino)        Zirconium(IV) (Zr(FH₂Ge-Cp)(NHnPr)₃);    -   the Germanium- and Zirconium-containing precursor being        (monofluorogermyl)cyclopentadienyl tris(Diisopropylamino)        Zirconium(IV) (Zr(FH₂Ge-Cp)(NiPr₂)₃);    -   the Germanium- and Zirconium-containing precursor being        (monofluorogermyl)cyclopentadienyl tris(isopropylamino)        Zirconium(IV) (Zr(FH₂Ge-Cp)(NHiPr)₃);    -   the Germanium- and Zirconium-containing precursor being        (monofluorogermyl)cyclopentadienyl tris(Di n-butylamino)        Zirconium(IV) (Zr(FH₂Ge-Cp)(NnBu₂)₃);    -   the Germanium- and Zirconium-containing precursor being        (monofluorogermyl)cyclopentadienyl tris(n-butylamino)        Zirconium(IV) (Zr(FH₂Ge-Cp)(NHnBu)₃);    -   the Germanium- and Zirconium-containing precursor being        (monofluorogermyl)cyclopentadienyl tris(Di isobutylamino)        Zirconium(IV) (Zr(FH₂Ge-Cp)(NiBu₂)₃);    -   the Germanium- and Zirconium-containing precursor being        (monofluorogermyl)cyclopentadienyl tris(isobutylamino)        Zirconium(IV) (Zr(FH₂Ge-Cp)(NHiBu)₃);    -   the Germanium- and Zirconium-containing precursor being        (monofluorogermyl)cyclopentadienyl tris(Di sec-butylamino)        Zirconium(IV) (Zr(FH₂Ge-Cp)(NsBu₂)₃);    -   the Germanium- and Zirconium-containing precursor being        (monofluorogermyl)cyclopentadienyl tris(sec-butylamino)        Zirconium(IV) (Zr(FH₂Ge-Cp)(NHsBu)₃);    -   the Germanium- and Zirconium-containing precursor being        (monofluorogermyl)cyclopentadienyl tris(Di tert-butylamino)        Zirconium(IV) (Zr(FH₂Ge-Cp)(NtBu₂)₃);    -   the Germanium- and Zirconium-containing precursor being        (monofluorogermyl)cyclopentadienyl tris(tert-butylamino)        Zirconium(IV) (Zr(FH₂Ge-Cp)(NHtBu)₃);    -   the Germanium- and Zirconium-containing precursor being        (monofluorogermyl)cyclopentadienyl tris(methoxy) Zirconium(IV)        (Zr(FH₂Ge-Cp)(OMe)₃);    -   the Germanium- and Zirconium-containing precursor being        (monofluorogermyl)cyclopentadienyl tris(ethoxy)Zirconium(IV)        (Zr(FH₂Ge-Cp)(OEt)₃);    -   the Germanium- and Zirconium-containing precursor being        (monofluorogermyl)cyclopentadienyl tris(n-propoxy) Zirconium(IV)        (Zr(FH₂Ge-Cp)(OnPr)₃);    -   the Germanium- and Zirconium-containing precursor being        (monofluorogermyl)cyclopentadienyl tris(isopropoxy)        Zirconium(IV) (Zr(FH₂Ge-Cp)(OiPr)₃);    -   the Germanium- and Zirconium-containing precursor being        (monofluorogermyl)cyclopentadienyl tris(tert-butoxy)        Zirconium(IV) (Zr(FH₂Ge-Cp)(OtBu)₃);    -   the Germanium- and Zirconium-containing precursor being        (monofluorogermyl)cyclopentadienyl tris(sec-butoxy)        Zirconium(IV) (Zr(FH₂Ge-Cp)(OsBu)₃);    -   the Germanium- and Zirconium-containing precursor being        (monofluorogermyl)cyclopentadienyl tris(n-butoxy) Zirconium(IV)        (Zr(FH₂Ge-Cp)(OnBu)₃);    -   the Germanium- and Zirconium-containing precursor being        (monofluorogermyl)cyclopentadienyl tris(isobutoxy) Zirconium(IV)        (Zr(FH₂Ge-Cp)(OiBu)₃);    -   the Germanium- and Zirconium-containing precursor being (fluoro        dimethylgermyl)cyclopentadienyl tris(Dimethylamino)        Zirconium(IV) (Zr(FMe₂Ge-Cp)(NMe₂)₃);    -   the Germanium- and Zirconium-containing precursor being (fluoro        dimethylgermyl)cyclopentadienyl tris(methylamino) Zirconium(IV)        (Zr(FMe₂Ge-Cp)(NHMe)₃);    -   the Germanium- and Zirconium-containing precursor being (fluoro        dimethylgermyl)cyclopentadienyl tris(Diethylamino) Zirconium(IV)        (Zr(FMe₂Ge-Cp)(NEt₂)₃);    -   the Germanium- and Zirconium-containing precursor being (fluoro        dimethylgermyl)cyclopentadienyl tris(ethylamino) Zirconium(IV)        (Zr(FMe₂Ge-Cp)(NHEt)₃);    -   the Germanium- and Zirconium-containing precursor being (fluoro        dimethylgermyl)cyclopentadienyl tris(Ethylmethylamino)        Zirconium(IV) (Zr(FMe₂Ge-Cp)(NEtMe)₃);    -   the Germanium- and Zirconium-containing precursor being (fluoro        dimethylgermyl)cyclopentadienyl tris(Di n-propylamino)        Zirconium(IV) (Zr(FMe₂Ge-Cp)(NnPr₂)₃);    -   the Germanium- and Zirconium-containing precursor being (fluoro        dimethylgermyl)cyclopentadienyl tris(n-propylamino)        Zirconium(IV) (Zr(FMe₂Ge-Cp)(NHnPr)₃);    -   the Germanium- and Zirconium-containing precursor being (fluoro        dimethylgermyl)cyclopentadienyl tris(Diisopropylamino)        Zirconium(IV) (Zr(FMe₂Ge-Cp)(NiPr₂)₃);    -   the Germanium- and Zirconium-containing precursor being (fluoro        dimethylgermyl)cyclopentadienyl tris(isopropylamino)        Zirconium(IV) (Zr(FMe₂Ge-Cp)(NHiPr)₃);    -   the Germanium- and Zirconium-containing precursor being (fluoro        dimethylgermyl)cyclopentadienyl tris(Di n-butylamino)        Zirconium(IV) (Zr(FMe₂Ge-Cp)(NnBu₂)₃);    -   the Germanium- and Zirconium-containing precursor being (fluoro        dimethylgermyl)cyclopentadienyl tris(n-butylamino) Zirconium(IV)        (Zr(FMe₂Ge-Cp)(NHnBu)₃);    -   the Germanium- and Zirconium-containing precursor being (fluoro        dimethylgermyl)cyclopentadienyl tris(Di isobutylamino)        Zirconium(IV) (Zr(FMe₂Ge-Cp)(NiBu₂)₃);    -   the Germanium- and Zirconium-containing precursor being (fluoro        dimethylgermyl)cyclopentadienyl tris(isobutylamino)        Zirconium(IV) (Zr(FMe₂Ge-Cp)(NHiBu)₃);    -   the Germanium- and Zirconium-containing precursor being (fluoro        dimethylgermyl)cyclopentadienyl tris(Di sec-butylamino)        Zirconium(IV) (Zr(FMe₂Ge-Cp)(NsBu₂)₃);    -   the Germanium- and Zirconium-containing precursor being (fluoro        dimethylgermyl)cyclopentadienyl tris(sec-butylamino)        Zirconium(IV) (Zr(FMe₂Ge-Cp)(NHsBu)₃);    -   the Germanium- and Zirconium-containing precursor being (fluoro        dimethylgermyl)cyclopentadienyl tris(Di tert-butylamino)        Zirconium(IV) (Zr(FMe₂Ge-Cp)(NtBu₂)₃);    -   the Germanium- and Zirconium-containing precursor being (fluoro        dimethylgermyl)cyclopentadienyl tris(tert-butylamino)        Zirconium(IV) (Zr(FMe₂Ge-Cp)(NHtBu)₃);    -   the Germanium- and Zirconium-containing precursor being (fluoro        dimethylgermyl)cyclopentadienyl tris(methoxy) Zirconium(IV)        (Zr(FMe₂Ge-Cp)(OMe)₃);    -   the Germanium- and Zirconium-containing precursor being (fluoro        dimethylgermyl)cyclopentadienyl tris(ethoxy) Zirconium(IV)        (Zr(FMe₂Ge-Cp)(OEt)₃);    -   the Germanium- and Zirconium-containing precursor being (fluoro        dimethylgermyl)cyclopentadienyl tris(n-propoxy) Zirconium(IV)        (Zr(FMe₂Ge-Cp)(OnPr)₃);    -   the Germanium- and Zirconium-containing precursor being (fluoro        dimethylgermyl)cyclopentadienyl tris(isopropoxy) Zirconium(IV)        (Zr(FMe₂Ge-Cp)(OiPr)₃);    -   the Germanium- and Zirconium-containing precursor being (fluoro        dimethylgermyl)cyclopentadienyl tris(tert-butoxy) Zirconium(IV)        (Zr(FMe₂Ge-Cp)(OtBu)₃);    -   the Germanium- and Zirconium-containing precursor being (fluoro        dimethylgermyl)cyclopentadienyl tris(sec-butoxy) Zirconium(IV)        (Zr(FMe₂Ge-Cp)(OsBu)₃);    -   the Germanium- and Zirconium-containing precursor being (fluoro        dimethylgermyl)cyclopentadienyl tris(n-butoxy) Zirconium(IV)        (Zr(FMe₂Ge-Cp)(OnBu)₃);    -   the Germanium- and Zirconium-containing precursor being (fluoro        dimethylgermyl)cyclopentadienyl tris(isobutoxy) Zirconium(IV)        (Zr(FMe₂Ge-Cp)(OiBu)₃);    -   the Germanium- and Zirconium-containing precursor being        (tris(trifluoromethyl)germyl)cyclopentadienyl        tris(Dimethylamino)Zirconium(IV) (Zr((CF₃)₃Ge-Cp)(NMe₂)₃);    -   the Germanium- and Zirconium-containing precursor being        (tris(trifluoromethyl)germyl)cyclopentadienyl tris(methylamino)        Zirconium(IV) (Zr((CF₃)₃Ge-Cp)(NHMe)₃);    -   the Germanium- and Zirconium-containing precursor being        (tris(trifluoromethyl)germyl)cyclopentadienyl tris(Diethylamino)        Zirconium(IV) (Zr((CF₃)₃Ge-Cp)(NEt₂)₃);    -   the Germanium- and Zirconium-containing precursor being        (tris(trifluoromethyl)germyl)cyclopentadienyl tris(ethylamino)        Zirconium(IV) (Zr((CF₃)₃Ge-Cp)(NHEt)₃);    -   the Germanium- and Zirconium-containing precursor being        (tris(trifluoromethyl)germyl)cyclopentadienyl        tris(Ethylmethylamino)Zirconium(IV) (Zr((CF₃)₃Ge-Cp)(NEtMe)₃);    -   the Germanium- and Zirconium-containing precursor being        (tris(trifluoromethyl)germyl)cyclopentadienyl tris(Di        n-propylamino)Zirconium(IV) (Zr((CF₃)₃Ge-Cp)(NnPr₂)₃);    -   the Germanium- and Zirconium-containing precursor being        (tris(trifluoromethyl)germyl)cyclopentadienyl        tris(n-propylamino)Zirconium(IV) (Zr((CF₃)₃Ge-Cp)(NHnPr)₃);    -   the Germanium- and Zirconium-containing precursor being        (tris(trifluoromethyl)germyl)cyclopentadienyl tris(Di        isopropylamino)Zirconium(IV) (Zr((CF₃)₃Ge-Cp)(NiPr₂)₃);    -   the Germanium- and Zirconium-containing precursor being        (tris(trifluoromethyl)germyl)cyclopentadienyl        tris(isopropylamino)Zirconium(IV) (Zr((CF₃)₃Ge-Cp)(NHiPr)₃);    -   the Germanium- and Zirconium-containing precursor being        (tris(trifluoromethyl)germyl)cyclopentadienyl tris(Di        n-butylamino)Zirconium(IV) (Zr((CF₃)₃Ge-Cp)(NnBu₂)₃);    -   the Germanium- and Zirconium-containing precursor being        (tris(trifluoromethyl)germyl)cyclopentadienyl tris(n-butylamino)        Zirconium(IV) (Zr((CF₃)₃Ge-Cp)(NHnBu)₃);    -   the Germanium- and Zirconium-containing precursor being        (tris(trifluoromethyl)germyl)cyclopentadienyl tris(Di        isobutylamino)Zirconium(IV) (Zr((CF₃)₃Ge-Cp)(NiBu₂)₃);    -   the Germanium- and Zirconium-containing precursor being        (tris(trifluoromethyl)germyl)cyclopentadienyl        tris(isobutylamino) Zirconium(IV) (Zr((CF₃)₃Ge-Cp)(NHiBu)₃);    -   the Germanium- and Zirconium-containing precursor being        (tris(trifluoromethyl)germyl)cyclopentadienyl tris(Di        sec-butylamino)Zirconium(IV) (Zr((CF₃)₃Ge-Cp)(NsBu₂)₃);    -   the Germanium- and Zirconium-containing precursor being        (tris(trifluoromethyl)germyl)cyclopentadienyl        tris(sec-butylamino)Zirconium(IV) (Zr((CF₃)₃Ge-Cp)(NHsBu)₃);    -   the Germanium- and Zirconium-containing precursor being        (tris(trifluoromethyl)germyl)cyclopentadienyl tris(Di        tert-butylamino)Zirconium(IV) (Zr((CF₃)₃Ge-Cp)(NtBu₂)₃);    -   the Germanium- and Zirconium-containing precursor being        (tris(trifluoromethyl)germyl)cyclopentadienyl        tris(tert-butylamino)Zirconium(IV) (Zr((CF₃)₃Ge-Cp)(NHtBu)₃);    -   the Germanium- and Zirconium-containing precursor being        (tris(trifluoromethyl)germyl)cyclopentadienyl tris(methoxy)        Zirconium(IV) (Zr((CF₃)₃Ge-Cp)(OMe)₃);    -   the Germanium- and Zirconium-containing precursor being        (tris(trifluoromethyl)germyl)cyclopentadienyl tris(ethoxy)        Zirconium(IV) (Zr((CF₃)₃Ge-Cp)(OEt)₃);    -   the Germanium- and Zirconium-containing precursor being        (tris(trifluoromethyl)germyl)cyclopentadienyl tris(n-propoxy)        Zirconium(IV) (Zr((CF₃)₃Ge-Cp)(OnPr)₃);    -   the Germanium- and Zirconium-containing precursor being        (tris(trifluoromethyl)germyl)cyclopentadienyl tris(isopropoxy)        Zirconium(IV) (Zr((CF₃)₃Ge-Cp)(OiPr)₃);    -   the Germanium- and Zirconium-containing precursor being        (tris(trifluoromethyl)germyl)cyclopentadienyl tris(tert-butoxy)        Zirconium(IV) (Zr((CF₃)₃Ge-Cp)(OtBu)₃);    -   the Germanium- and Zirconium-containing precursor being        (tris(trifluoromethyl)germyl)cyclopentadienyl tris(sec-butoxy)        Zirconium(IV) (Zr((CF₃)₃Ge-Cp)(OsBu)₃);    -   the Germanium- and Zirconium-containing precursor being        (tris(trifluoromethyl)germyl)cyclopentadienyl tris(n-butoxy)        Zirconium(IV) (Zr((CF₃)₃Ge-Cp)(OnBu)₃);    -   the Germanium- and Zirconium-containing precursor being        (tris(trifluoromethyl)germyl)cyclopentadienyl tris(isobutoxy)        Zirconium(IV) (Zr((CF₃)₃Ge-Cp)(OiBu)₃);    -   the Germanium- and Zirconium-containing precursor being        (bis(trifluoromethyl)germyl)cyclopentadienyl        tris(Dimethylamino)Zirconium(IV) (Zr((CF₃)₂HGe-Cp)(NMe₂)₃);    -   the Germanium- and Zirconium-containing precursor being        (bis(trifluoromethyl)germyl)cyclopentadienyl tris(methylamino)        Zirconium(IV) (Zr((CF₃)₂HGe-Cp)(NHMe)₃);    -   the Germanium- and Zirconium-containing precursor being        (bis(trifluoromethyl)germyl)cyclopentadienyl tris(Diethylamino)        Zirconium(IV) (Zr((CF₃)₂HGe-Cp)(NEt₂)₃);    -   the Germanium- and Zirconium-containing precursor being        (bis(trifluoromethyl)germyl)cyclopentadienyl tris(ethylamino)        Zirconium(IV) (Zr((CF₃)₂HGe-Cp)(NHEt)₃);    -   the Germanium- and Zirconium-containing precursor being        (bis(trifluoromethyl)germyl)cyclopentadienyl        tris(Ethylmethylamino)Zirconium(IV) (Zr((CF₃)₂HGe-Cp)(NEtMe)₃);    -   the Germanium- and Zirconium-containing precursor being        (bis(trifluoromethyl)germyl)cyclopentadienyl tris(Di        n-propylamino)Zirconium(IV) (Zr((CF₃)₂HGe-Cp)(NnPr₂)₃);    -   the Germanium- and Zirconium-containing precursor being        (bis(trifluoromethyl)germyl)cyclopentadienyl tris(n-propylamino)        Zirconium(IV) (Zr((CF₃)₂HGe-Cp)(NHnPr)₃);    -   the Germanium- and Zirconium-containing precursor being        (bis(trifluoromethyl)germyl)cyclopentadienyl tris(Di        isopropylamino)Zirconium(IV) (Zr((CF₃)₂HGe-Cp)(NiPr₂)₃);    -   the Germanium- and Zirconium-containing precursor being        (bis(trifluoromethyl)germyl)cyclopentadienyl        tris(isopropylamino)Zirconium(IV) (Zr((CF₃)₂HGe-Cp)(NHiPr)₃);    -   the Germanium- and Zirconium-containing precursor being        (bis(trifluoromethyl)germyl)cyclopentadienyl tris(Di        n-butylamino)Zirconium(IV) (Zr((CF₃)₂HGe-Cp)(NnBu₂)₃);    -   the Germanium- and Zirconium-containing precursor being        (bis(trifluoromethyl)germyl)cyclopentadienyl tris(n-butylamino)        Zirconium(IV) (Zr((CF₃)₂HGe-Cp)(NHnBu)₃);    -   the Germanium- and Zirconium-containing precursor being        (bis(trifluoromethyl)germyl)cyclopentadienyl tris(Di        isobutylamino)Zirconium(IV) (Zr((CF₃)₂HGe-Cp)(NiBu₂)₃);    -   the Germanium- and Zirconium-containing precursor being        (bis(trifluoromethyl)germyl)cyclopentadienyl tris(isobutylamino)        Zirconium(IV) (Zr((CF₃)₂HGe-Cp)(NHiBu)₃);    -   the Germanium- and Zirconium-containing precursor being        (bis(trifluoromethyl)germyl)cyclopentadienyl tris(Di        sec-butylamino)Zirconium(IV) (Zr((CF₃)₂HGe-Cp)(NsBu₂)₃);    -   the Germanium- and Zirconium-containing precursor being        (bis(trifluoromethyl)germyl)cyclopentadienyl        tris(sec-butylamino)Zirconium(IV) (Zr((CF₃)₂HGe-Cp)(NHsBu)₃);    -   the Germanium- and Zirconium-containing precursor being        (bis(trifluoromethyl)germyl)cyclopentadienyl tris(Di        tert-butylamino)Zirconium(IV) (Zr((CF₃)₂HGe-Cp)(NtBu₂)₃);    -   the Germanium- and Zirconium-containing precursor being        (bis(trifluoromethyl)germyl)cyclopentadienyl        tris(tert-butylamino)Zirconium(IV) (Zr((CF₃)₂HGe-Cp)(NHtBu)₃);    -   the Germanium- and Zirconium-containing precursor being        (bis(trifluoromethyl)germyl)cyclopentadienyl tris(methoxy)        Zirconium(IV) (Zr((CF₃)₂HGe-Cp)(OMe)₃);    -   the Germanium- and Zirconium-containing precursor being        (bis(trifluoromethyl)germyl)cyclopentadienyl tris(ethoxy)        Zirconium(IV) (Zr((CF₃)₂HGe-Cp)(OEt)₃);    -   the Germanium- and Zirconium-containing precursor being        (bis(trifluoromethyl)germyl)cyclopentadienyl tris(n-propoxy)        Zirconium(IV) (Zr((CF₃)₂HGe-Cp)(OnPr)₃);    -   the Germanium- and Zirconium-containing precursor being        (bis(trifluoromethyl)germyl)cyclopentadienyl tris(isopropoxy)        Zirconium(IV) (Zr((CF₃)₂HGe-Cp)(OiPr)₃);    -   the Germanium- and Zirconium-containing precursor being        (bis(trifluoromethyl)germyl)cyclopentadienyl tris(tert-butoxy)        Zirconium(IV) (Zr((CF₃)₂HGe-Cp)(OtBu)₃);    -   the Germanium- and Zirconium-containing precursor being        (bis(trifluoromethyl)germyl)cyclopentadienyl tris(sec-butoxy)        Zirconium(IV) (Zr((CF₃)₂HGe-Cp)(OsBu)₃);    -   the Germanium- and Zirconium-containing precursor being        (bis(trifluoromethyl)germyl)cyclopentadienyl tris(n-butoxy)        Zirconium(IV) (Zr((CF₃)₂HGe-Cp)(OnBu)₃);    -   the Germanium- and Zirconium-containing precursor being        (bis(trifluoromethyl)germyl)cyclopentadienyl tris(iso-butoxy)        Zirconium(IV) (Zr((CF₃)₂HGe-Cp)(OiBu)₃);    -   the Germanium- and Zirconium-containing precursor being        ((trifluoromethyl)dimethylgermyl)cyclopentadienyl        tris(Dimethylamino)Zirconium(IV) (Zr((CF₃)Me₂Ge-Cp)(NMe₂)₃);    -   the Germanium- and Zirconium-containing precursor being        ((trifluoromethyl)dimethylgermyl)cyclopentadienyl        tris(methylamino)Zirconium(IV) (Zr((CF₃)Me₂Ge-Cp)(NHMe)₃);    -   the Germanium- and Zirconium-containing precursor being        ((trifluoromethyl)dimethylgermyl)cyclopentadienyl        tris(Diethylamino)Zirconium(IV) (Zr((CF₃)Me₂Ge-Cp)(NEt₂)₃);    -   the Germanium- and Zirconium-containing precursor being        ((trifluoromethyl)dimethylgermyl)cyclopentadienyl        tris(ethylamino)Zirconium(IV) (Zr((CF₃)Me₂Ge-Cp)(NHEt)₃);    -   the Germanium- and Zirconium-containing precursor being        ((trifluoromethyl)dimethylgermyl)cyclopentadienyl        tris(Ethylmethylamino)Zirconium(IV) (Zr((CF₃)Me₂Ge-Cp)(NEtMe)₃);    -   the Germanium- and Zirconium-containing precursor being        ((trifluoromethyl)dimethylgermyl)cyclopentadienyl tris(Di        n-propylamino)Zirconium(IV) (Zr((CF₃)Me₂Ge-Cp)(NnPr₂)₃);    -   the Germanium- and Zirconium-containing precursor being        ((trifluoromethyl)dimethylgermyl)cyclopentadienyl        tris(n-propylamino)Zirconium(IV) (Zr((CF₃)Me₂Ge-Cp)(NHnPr)₃);    -   the Germanium- and Zirconium-containing precursor being        ((trifluoromethyl)dimethylgermyl)cyclopentadienyl tris(Di        isopropylamino)Zirconium(IV) (Zr((CF₃)Me₂Ge-Cp)(NiPr₂)₃);    -   the Germanium- and Zirconium-containing precursor being        ((trifluoromethyl)dimethylgermyl)cyclopentadienyl        tris(isopropylamino)Zirconium(IV) (Zr((CF₃)Me₂Ge-Cp)(NHiPr)₃);    -   the Germanium- and Zirconium-containing precursor being        ((trifluoromethyl)dimethylgermyl)cyclopentadienyl tris(Di        n-butylamino)Zirconium(IV) (Zr((CF₃)Me₂Ge-Cp)(NnBu₂)₃);    -   the Germanium- and Zirconium-containing precursor being        ((trifluoromethyl)dimethylgermyl)cyclopentadienyl        tris(n-butylamino)Zirconium(IV) (Zr((CF₃)Me₂Ge-Cp)(NHnBu)₃);    -   the Germanium- and Zirconium-containing precursor being        ((trifluoromethyl)dimethylgermyl)cyclopentadienyl tris(Di        isobutylamino)Zirconium(IV) (Zr((CF₃)Me₂Ge-Cp)(NiBu₂)₃);    -   the Germanium- and Zirconium-containing precursor being        ((trifluoromethyl)dimethylgermyl)cyclopentadienyl        tris(isobutylamino)Zirconium(IV) (Zr((CF₃)Me₂Ge-Cp)(NHiBu)₃);    -   the Germanium- and Zirconium-containing precursor being        ((trifluoromethyl)dimethylgermyl)cyclopentadienyl tris(Di        sec-butylamino)Zirconium(IV) (Zr((CF₃)Me₂Ge-Cp)(NsBu₂)₃);    -   the Germanium- and Zirconium-containing precursor being        ((trifluoromethyl)dimethylgermyl)cyclopentadienyl        tris(sec-butylamino)Zirconium(IV) (Zr((CF₃)Me₂Ge-Cp)(NHsBu)₃);    -   the Germanium- and Zirconium-containing precursor being        ((trifluoromethyl)dimethylgermyl)cyclopentadienyl tris(Di        tert-butylamino)Zirconium(IV) (Zr((CF₃)Me₂Ge-Cp)(NtBu₂)₃);    -   the Germanium- and Zirconium-containing precursor being        ((trifluoromethyl)dimethylgermyl)cyclopentadienyl        tris(tert-butylamino)Zirconium(IV) (Zr((CF₃)Me₂Ge-Cp)(NHtBu)₃);    -   the Germanium- and Zirconium-containing precursor being        ((trifluoromethyl)dimethylgermyl)cyclopentadienyl tris(methoxy)        Zirconium(IV) (Zr((CF₃)Me₂Ge-Cp)(OMe)₃);    -   the Germanium- and Zirconium-containing precursor being        ((trifluoromethyl)dimethylgermyl)cyclopentadienyl tris(ethoxy)        Zirconium(IV) (Zr((CF₃)Me₂Ge-Cp)(OEt)₃);    -   the Germanium- and Zirconium-containing precursor being        ((trifluoromethyl)dimethylgermyl)cyclopentadienyl        tris(n-propoxy)Zirconium(IV) (Zr((CF₃)Me₂Ge-Cp)(OnPr)₃);    -   the Germanium- and Zirconium-containing precursor being        ((trifluoromethyl)dimethylgermyl)cyclopentadienyl        tris(isopropoxy)Zirconium(IV) (Zr((CF₃)Me₂Ge-Cp)(OiPr)₃);    -   the Germanium- and Zirconium-containing precursor being        ((trifluoromethyl)dimethylgermyl)cyclopentadienyl        tris(tert-butoxy)Zirconium(IV) (Zr((CF₃)Me₂Ge-Cp)(OtBu)₃);    -   the Germanium- and Zirconium-containing precursor being        ((trifluoromethyl)dimethylgermyl)cyclopentadienyl        tris(sec-butoxy)Zirconium(IV) (Zr((CF₃)Me₂Ge-Cp)(OsBu)₃);    -   the Germanium- and Zirconium-containing precursor being        ((trifluoromethyl)dimethylgermyl)cyclopentadienyl tris(n-butoxy)        Zirconium(IV) (Zr((CF₃)Me₂Ge-Cp)(OnBu)₃);    -   the Germanium- and Zirconium-containing precursor being        ((trifluoromethyl)dimethylgermyl)cyclopentadienyl        tris(isobutoxy)Zirconium(IV) (Zr((CF₃)Me₂Ge-Cp)(OiBu)₃);    -   the Germanium- and Zirconium-film forming composition comprising        between approximately 95% w/w and approximately 100% w/w of the        precursor;    -   the Germanium- and Zirconium-film forming composition comprising        between approximately 98% w/w and approximately 100% w/w of the        precursor;    -   the Germanium- and Zirconium-film forming composition comprising        between approximately 99% w/w and approximately 100% w/w of the        precursor;    -   the Germanium- and Zirconium-film forming composition comprising        between approximately 0.0% w/w and approximately 5.0% w/w        impurities;    -   the Germanium- and Zirconium-film forming composition comprising        between approximately 0.0% w/w and approximately 2.0% w/w        impurities;    -   the Germanium- and Zirconium-film forming composition comprising        between approximately 0.0% w/w and approximately 1.0% w/w        impurities;    -   the impurities including alcohol; alkylamines; dialkylamines;        alkylimines; cyclopentadiene; dicyclopentadiene; alkylgermane;        THF; ether; pentane; cyclohexane; heptanes; benzene; toluene;        chlorinated metal compounds; lithium, sodium, or potassium        alkylamino; lithium, sodium, or potassium alkoxy; and lithium,        sodium, or potassium cyclopentadienyl;    -   the Germanium- and Zirconium-film forming composition comprising        between approximately 0.0% w/w and approximately 2.0% w/w        alkylamine impurities;    -   the Germanium- and Zirconium-film forming composition comprising        between approximately 0.0% w/w and approximately 2.0% w/w        alkylimine impurities;    -   the Germanium- and Zirconium-film forming composition comprising        between approximately 0.0% w/w and approximately 2.0% w/w        alcohol impurities;    -   the Germanium- and Zirconium-film forming composition comprising        between approximately 0.0% w/w and approximately 2.0% w/w        cyclopentadiene impurities;    -   the Germanium- and Zirconium-film forming composition comprising        between approximately 0.0% w/w and approximately 2.0% w/w        dicyclopentadiene impurities;    -   the Germanium- and Zirconium-film forming composition comprising        between approximately 0.0% w/w and approximately 2.0% w/w        alkylgermane impurities;    -   the Germanium- and Zirconium-film forming composition comprising        between approximately 0.0% w/w and approximately 2.0% w/w THF        impurities;    -   the Germanium- and Zirconium-film forming composition comprising        between approximately 0.0% w/w and approximately 2.0% w/w ether        impurities;    -   the Germanium- and Zirconium-film forming composition comprising        between approximately 0.0% w/w and approximately 2.0% w/w        pentane impurities;    -   the Germanium- and Zirconium-film forming composition comprising        between approximately 0.0% w/w and approximately 2.0% w/w        cyclohexane impurities;    -   the Germanium- and Zirconium-film forming composition comprising        between approximately 0.0% w/w and approximately 2.0% w/w        heptanes impurities;    -   the Germanium- and Zirconium-film forming composition comprising        between approximately 0.0% w/w and approximately 2.0% w/w        benzene impurities;    -   the Germanium- and Zirconium-film forming composition comprising        between approximately 0.0% w/w and approximately 2.0% w/w        toluene impurities;    -   the Germanium- and Zirconium-film forming composition comprising        between approximately 0.0% w/w and approximately 2.0% w/w        chlorinated metal compound impurities;    -   the Germanium- and Zirconium-film forming composition comprising        between approximately 0.0% w/w and approximately 2.0% w/w        lithium, sodium, or potassium cyclopentadienyl impurities;    -   the Germanium- and Zirconium-film forming composition comprising        between approximately 0.0% w/w and approximately 2.0% w/w        lithium, sodium, or potassium alkylamino impurities;    -   the Germanium- and Zirconium-film forming composition comprising        between approximately 0.0% w/w and approximately 2.0% w/w        lithium, sodium, or potassium alkoxy impurities;    -   the Germanium- and Zirconium-film forming composition comprising        between approximately 0 ppbw and approximately 1 ppmw metal        impurities;    -   the Germanium- and Zirconium-film forming composition comprising        between approximately 0 ppbw and approximately 500 ppbw metal        impurities;    -   the metal impurities including Aluminum (Al), Arsenic (As),        Barium (Ba), Beryllium (Be), Bismuth (Bi), Cadmium (Cd), Calcium        (Ca), Chromium (Cr), Cobalt (Co), Copper (Cu), Gallium (Ga),        Germanium (Ge), Hafnium (Hf), Zirconium (Zr), Indium (In), Iron        (Fe), Lead (Pb), Lithium (Li), Magnesium (Mg), Manganese (Mn),        Tungsten (W), Nickel (Ni), Potassium (K), Sodium (Na), Strontium        (Sr), Thorium (Th), Tin (Sn), Titanium (Ti), Uranium (U), and        Zinc (Zn);    -   the Germanium- and Zirconium-film forming composition comprising        between approximately 0 ppbw and approximately 500 ppbw Al        impurities;    -   the Germanium- and Zirconium-film forming composition comprising        between approximately 0 ppbw and approximately 500 ppbw As        impurities;    -   the Germanium- and Zirconium-film forming composition comprising        between approximately 0 ppbw and approximately 500 ppbw Ba        impurities;    -   the Germanium- and Zirconium-film forming composition comprising        between approximately 0 ppbw and approximately 500 ppbw Be        impurities;    -   the Germanium- and Zirconium-film forming composition comprising        between approximately 0 ppbw and approximately 500 ppbw Bi        impurities;    -   the Germanium- and Zirconium-film forming composition comprising        between approximately 0 ppbw and approximately 500 ppbw Cd        impurities;    -   the Germanium- and Zirconium-film forming composition comprising        between approximately 0 ppbw and approximately 500 ppbw Ca        impurities;    -   the Germanium- and Zirconium-film forming composition comprising        between approximately 0 ppbw and approximately 500 ppbw Cr        impurities;    -   the Germanium- and Zirconium-film forming composition comprising        between approximately 0 ppbw and approximately 500 ppbw Co        impurities;    -   the Germanium- and Zirconium-film forming composition comprising        between approximately 0 ppbw and approximately 500 ppbw Cu        impurities;    -   the Germanium- and Zirconium-film forming composition comprising        between approximately 0 ppbw and approximately 500 ppbw Ga        impurities;    -   the Germanium- and Zirconium-film forming composition comprising        between approximately 0 ppbw and approximately 500 ppbw Ge        impurities;    -   the Germanium- and Zirconium-film forming composition comprising        between approximately 0 ppbw and approximately 500 ppbw Hf        impurities;    -   the Germanium- and Zirconium-film forming composition comprising        between approximately 0 ppbw and approximately 500 ppbw Zr        impurities;    -   the Germanium- and Zirconium-film forming composition comprising        between approximately 0 ppbw and approximately 500 ppbw In        impurities;    -   the Germanium- and Zirconium-film forming composition comprising        between approximately 0 ppbw and approximately 500 ppbw Fe        impurities;    -   the Germanium- and Zirconium-film forming composition comprising        between approximately 0 ppbw and approximately 500 ppbw Pb        impurities;    -   the Germanium- and Zirconium-film forming composition comprising        between approximately 0 ppbw and approximately 500 ppbw Li        impurities;    -   the Germanium- and Zirconium-film forming composition comprising        between approximately 0 ppbw and approximately 500 ppbw Mg        impurities;    -   the Germanium- and Zirconium-film forming composition comprising        between approximately 0 ppbw and approximately 500 ppbw Mn        impurities;    -   the Germanium- and Zirconium-film forming composition comprising        between approximately 0 ppbw and approximately 500 ppbw W        impurities;    -   the Germanium- and Zirconium-film forming composition comprising        between approximately 0 ppbw and approximately 500 ppbw Ni        impurities;    -   the Germanium- and Zirconium-film forming composition comprising        between approximately 0 ppbw and approximately 500 ppbw K        impurities;    -   the Germanium- and Zirconium-film forming composition comprising        between approximately 0 ppbw and approximately 500 ppbw Na        impurities;    -   the Germanium- and Zirconium-film forming composition comprising        between approximately 0 ppbw and approximately 500 ppbw Sr        impurities;    -   the Germanium- and Zirconium-film forming composition comprising        between approximately 0 ppbw and approximately 500 ppbw Th        impurities;    -   the Germanium- and Zirconium-film forming composition comprising        between approximately 0 ppbw and approximately 500 ppbw Sn        impurities;    -   the Germanium- and Zirconium-film forming composition comprising        between approximately 0 ppbw and approximately 500 ppbw Ti        impurities;    -   the Germanium- and Zirconium-film forming composition comprising        between approximately 0 ppbw and approximately 500 ppbw U        impurities; and    -   the Germanium- and Zirconium-film forming composition comprising        between approximately 0 ppbw and approximately 500 ppbw Zn        impurities.

Also disclosed are processes for the deposition of Zirconium-containingfilms on substrates. The Germanium- and Zirconium-film formingcompositions disclosed above are introduced into a reactor having asubstrate disposed therein. At least part of the precursor is depositedonto the substrate to form the Zirconium-containing film. The disclosedprocesses may further include one or more of the following aspects:

-   -   introducing a reactant into the reactor;    -   the reactant being plasma-treated;    -   the reactant being remote plasma-treated;    -   the reactant not being plasma-treated;    -   the reactant being selected from the group consisting of H₂,        H₂CO, N₂H₄, NH₃, SiH₄, Si₂H₆, Si₃H₈, SiH₂Me₂, SiH₂Et₂, N(SiH₃)₃,        hydrogen radicals thereof, and mixtures thereof;    -   the reactant being H₂;    -   the reactant being NH₃;    -   the reactant being selected from the group consisting of O₂, O₃,        H₂O, H₂O₂, NO, N₂O, NO₂, oxygen radicals thereof, and mixtures        thereof;    -   the reactant being H₂O;    -   the reactant being plasma treated O₂;    -   the reactant being O₃;    -   the reactant being a Zirconium-containing precursor;    -   the Zirconium-containing precursor being selected from the group        consisting of ZrCp(NMe₂)₃, Zr(MeCp)(NMe₂)₃, Zr(EtCp)(NMe₂)₃,        Zr(iPrCp)(NMe₂)₃, Zr(tBuCp)(NMe₂)₃, Zr(Cp)(NMeEt)₃;    -   the Zirconium-containing precursor being ZrCp(NMe₂)₃;    -   mixing the Germanium- and Zirconium-film forming composition and        the Zirconium-containing precursor to form a mixture prior to        introduction into the reactor;    -   the Germanium- and Zirconium-film forming composition and the        reactant being introduced into the reactor simultaneously;    -   the reactor being configured for chemical vapor deposition;    -   the reactor being configured for plasma enhanced chemical vapor        deposition;    -   the Germanium- and Zirconium-film forming composition and the        reactant being introduced into the chamber sequentially;    -   the reactor being configured for atomic layer deposition;    -   the reactor being configured for plasma enhanced atomic layer        deposition;    -   the reactor being configured for spatial atomic layer        deposition;    -   the Zirconium-containing film being a pure Zirconium film;    -   the pure Zirconium film having a Zr concentration between        approximately 95 atomic % to approximately 100 atomic %;    -   the Zirconium-containing film being a Zirconium silicide        (Zr_(k)Si_(l), wherein each of k and l is an integer which        inclusively range from 1 to 6);    -   the Zirconium silicide being ZrSi₂;    -   the Zirconium-containing film being a Zirconium oxide        (Zr_(m)O_(n), wherein each of m and n is an integer which        inclusively range from 1 to 6);    -   the zirconium oxide being ZrO₂;    -   the Zirconium-containing film being a Germanium-doped Zirconium        oxide (Zr_(o)Ge_(p)O_(q)), wherein each o and p is a decimal        which inclusively ranges from 0 to 1 and q is an integer which        inclusively ranges from 1 to 6);    -   the silicon-doped Zirconium oxide being        Zr_((0.99 to 0.5))Ge_((0.5 to 0.01))O₂;    -   the Zirconium-containing film being a Zirconium nitride        (Zr_(u)N_(v), wherein each of u and v is an integer which        inclusively range from 1 to 6); and    -   the Zirconium nitride being ZrN.

NOTATION AND NOMENCLATURE

Certain abbreviations, symbols, and terms are used throughout thefollowing description and claims, and include:

As used herein, the indefinite article “a” or “an” means one or more.

As used herein, the terms “approximately” or “about” mean±10% of thevalue stated.

As used herein, the term “independently” when used in the context ofdescribing R groups should be understood to denote that the subject Rgroup is not only independently selected relative to other R groupsbearing the same or different subscripts or superscripts, but is alsoindependently selected relative to any additional species of that same Rgroup. For example in the formula Zr(TMGCp)(NR¹R²)₃, the three R¹ groupsmay, but need not be identical to each other or to R².

As used herein, the term “alkyl group” refers to saturated functionalgroups containing exclusively carbon and hydrogen atoms. Further, theterm “alkyl group” refers to linear, branched, or cyclic alkyl groups.Examples of linear alkyl groups include without limitation, methylgroups, ethyl groups, propyl groups, butyl groups, etc. Examples ofbranched alkyls groups include without limitation, t-butyl. Examples ofcyclic alkyl groups include without limitation, cyclopropyl groups,cyclopentyl groups, cyclohexyl groups, etc.

As used herein, the abbreviation “Me” refers to a methyl group; theabbreviation “Et” refers to an ethyl group; the abbreviation “Pr” refersto a propyl group; the abbreviation “nPr” refers to a “normal” or linearpropyl group; the abbreviation “iPr” refers to an isopropyl group; theabbreviation “Bu” refers to a butyl group; the abbreviation “nBu” refersto a “normal” or linear butyl group; the abbreviation “tBu” refers to atert-butyl group, also known as 1,1-dimethylethyl; the abbreviation“sBu” refers to a sec-butyl group, also known as 1-methylpropyl; theabbreviation “iBu” refers to an iso-butyl group, also known as2-methylpropyl; the abbreviation “amyl” refers to an amyl or pentylgroup; the abbreviation “tAmyl” refers to a tert-amyl group, also knownas 1,1-dimethylpropyl; the abbreviation “Cp” refers to cyclopentadienyl;the abbreviation “Cp*” refers to pentamethylcyclopentadienyl; theabbreviation “op” refers to (open)pentadienyl; the abbreviation “TMGCp”refers to the ligand (trimethylgermyl)cyclopentadienyl [Me₃GeCp]; theabbreviation “TMGCpH” refers to the molecule(trimethylgermyl)cyclopentadiene [Me₃GeCpH]; the abbreviation DMGCprefers to the ligand (dimethylgermyl)cyclopentadienyl [Me₂HGeCp]; theabbreviation “TMSCp” refers to the ligand(trimethylsilyl)cyclopentadienyl [Me₃SiCp]; and the abbreviation“TMSCpH” refers to the molecule (trimethylsilyl)cyclopentadiene[Me₃SiCpH].

The standard abbreviations of the elements from the periodic table ofelements are used herein. It should be understood that elements may bereferred to by these abbreviations (e.g., Ge refers to germanium, Sirefers to silicon, C refers to carbon, etc.).

BRIEF DESCRIPTION OF THE FIGURES

For a further understanding of the nature and objects of the presentinvention, reference should be made to the following detaileddescription, taken in conjunction with the accompanying figure wherein:

FIG. 1 is a ¹HNMR spectrum of Zr(TMGCp)(NMe₂)₃;

FIG. 2 is a ¹HNMR spectrum of Zr(TMGCp)(OiPr)₃;

FIG. 3 is a ThermoGravimetric Analysis (TGA)/Differential ThermalAnalysis (DTA) graph demonstrating the percentage of weight loss (TGA)or the differential temperature (DTA) with increasing temperature ofZr(TMGCp)(NMe₂)₃; and

FIG. 4 is a TGA/DTA graph demonstrating the percentage of weight loss(TGA) or the differential temperature (DTA) with increasing temperatureof Zr(TMGCp)(OiPr)₃.

DESCRIPTION OF PREFERRED EMBODIMENTS

Disclosed are Germanium- and Zirconium-film forming compositionscomprising a Germanium- and Zirconium-containing precursor having thefollowing formula:

wherein each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹ and R¹⁰ is independentlyselected from H; a C1-C5 linear, branched, or cyclic alkyl group; or aC1-C5 linear, branched, or cyclic fluoroalkyl group. R¹, R² and R³ maybe identical or different. R⁴, R⁵, R⁶ and R⁷ may be identical ordifferent. R⁸ and R⁹ may be identical or different.

Preferably R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ are H or Me because smalleralkyl groups may increase the volatility and decrease the melting pointof the germanium- and zirconium-containing compound. Preferably R⁸ andR⁹ are H, Me or Et because smaller alkyl groups may increase thevolatility and decrease the melting point of the germanium- andzirconium-containing compound. Preferably R¹⁰ is Me, Et, iPr or tBubecause the smaller alkyl groups (Me, Et) may increase the volatilityand the larger alkyl groups (iPr, tBu) may decrease the melting point ofthe germanium- and zirconium-containing precursor.

Exemplary Germanium- and Zirconium-containing precursors of Formula Iinclude but are not limited to Zr(TMG-Cp)(NMe₂)₃, Zr(TMG-Cp)(NHMe)₃,Zr(TMG-Cp)(NEt₂)₃, Zr(TMG-Cp)(NHEt)₃, Zr(TMG-Cp)(NEtMe)₃),Zr(TMG-Cp)(NnPr₂)₃, Zr(TMG-Cp)(NHnPr)₃, Zr(TMG-Cp)(NiPr₂)₃,Zr(TMG-Cp)(NHiPr)₃, Zr(TMG-Cp)(NnBu₂)₃), Zr(TMG-Cp)(NHnBu)₃,Zr(TMG-Cp)(NiBu₂)₃, Zr(TMG-Cp)(NHiBu)₃, Zr(TMG-Cp)(NsBu₂)₃,Zr(TMSG-Cp)(NHsBu)₃, Zr(TMG-Cp)(NtBu₂)₃, Zr(TMG-Cp)(NHtBu)₃,Zr(DMG-Cp)(NMe₂)₃, Zr(DMG-Cp)(NHMe)₃, Zr(DMG-Cp)(NEt₂)₃,Zr(DMG-Cp)(NHEt)₃, Zr(DMG-Cp)(NEtMe)₃, Zr(DMG-Cp)(NnPr₂)₃,Zr(DMG-Cp)(NHnPr)₃, Zr(DMG-Cp)(NiPr₂)₃, Zr(DMG-Cp)(NHiPr)₃,Zr(DMG-Cp)(NnBu₂)₃, Zr(DMG-Cp)(NHnBu)₃, Zr(DMG-Cp)(NiBu₂)₃,Zr(DMG-Cp)(NHiBu)₃, Zr(DMG-Cp)(NsBu₂)₃, Zr(DMG-Cp)(NHsBu)₃,Zr(DMG-Cp)(NtBu₂)₃, Zr(DMG-Cp)(NHtBu)₃, Zr(F₃Ge-Cp)(NMe₂)₃,Zr(F₃Ge-Cp)(NHMe)₃, Zr(F₃Ge-Cp)(NEt₂)₃, Zr(F₃Ge-Cp)(NHEt)₃,Zr(F₃Ge-Cp)(NEtMe)₃, Zr(F₃Ge-Cp)(NnPr₂)₃, Zr(F₃Ge-Cp)(NHnPr)₃,Zr(F₃Ge-Cp)(NiPr₂)₃, Zr(F₃Ge-Cp)(NHiPr)₃, Zr(F₃Ge-Cp)(NnBu₂)₃,Zr(F₃Ge-Cp)(NHnBu)₃, Zr(F₃Ge-Cp)(NiBu₂)₃, Zr(F₃Ge-Cp)(NHiBu)₃,Zr(F₃Ge-Cp)(NsBu₂)₃, Zr(F₃Ge-Cp)(NHsBu)₃, Zr(F₃Ge-Cp)(NtBu₂)₃,Zr(F₃Ge-Cp)(NHtBu)₃, Zr(F₂HGe-Cp)(NMe₂)₃, Zr(F₂HGe-Cp)(NHMe)₃,Zr(F₂HGe-Cp)(NEt₂)₃, Zr(F₂HGe-Cp)(NHEt)₃, Zr(F₂HGe-Cp)(NEtMe)₃,Zr(F₂HGe-Cp)(NnPr₂)₃, Zr(F₂HGe-Cp)(NHnPr)₃, Zr(F₂HGe-Cp)(N iPr₂)₃,Zr(F₂HGe-Cp)(NHiPr)₃, Zr(F₂HGe-Cp)(NnBu₂)₃, Zr(F₂HGe-Cp)(NHnBu)₃,Zr(F₂HGe-Cp)(NiBu₂)₃, Zr(F₂HGe-Cp)(NHiBu)₃, Zr(F₂HGe-Cp)(NsBu₂)₃,Zr(F₂HGe-Cp)(NHsBu)₃, Zr(F₂HGe-Cp)(NtBu₂)₃, Zr(F₂HGe-Cp)(NHtBu)₃,Zr(FH₂Ge-Cp)(NMe₂)₃, Zr(FH₂Ge-Cp)(NHMe)₃, Zr(FH₂Ge-Cp)(NEt₂)₃,Zr(FH₂Ge-Cp)(NHEt)₃, Zr(FH₂Ge-Cp)(NEtMe)₃, Zr(FH₂Ge-Cp)(NnPr₂)₃,Zr(FH₂Ge-Cp)(NHnPr)₃, Zr(FH₂Ge-Cp)(NiPr₂)₃, Zr(FH₂Ge-Cp)(NHiPr)₃,Zr(FH₂Ge-Cp)(NnBu₂)₃, Zr(FH₂Ge-Cp)(NHnBu)₃, Zr(FH₂Ge-Cp)(NiBu₂)₃,Zr(FH₂Ge-Cp)(NHiBu)₃, Zr(FH₂Ge-Cp)(NsBu₂)₃, Zr(FH₂Ge-Cp)(NHsBu)₃,Zr(FH₂Ge-Cp)(NtBu₂)₃, Zr(FH₂Ge-Cp)(NHtBu)₃, Zr(FMe₂Ge-Cp)(NMe₂)₃,Zr(FMe₂Ge-Cp)(NHMe)₃, Zr(FMe₂Ge-Cp)(NEt₂)₃, Zr(FMe₂Ge-Cp)(NHEt)₃,Zr(FMe₂Ge-Cp)(NEtMe)₃, Zr(FMe₂Ge-Cp)(NnPr₂)₃, Zr(FMe₂Ge-Cp)(NHnPr)₃,Zr(FMe₂Ge-Cp)(NiPr₂)₃, Zr(FMe₂Ge-Cp)(NHiPr)₃, Zr(FMe₂Ge-Cp)(NnBu₂)₃,Zr(FMe₂Ge-Cp)(NHnBu)₃, Zr(FMe₂Ge-Cp)(NiBu₂)₃, Zr(FMe₂Ge-Cp)(NHiBu)₃,Zr(FMe₂Ge-Cp)(NsBu₂)₃, Zr(FMe₂Ge-Cp)(NHsBu)₃, Zr(FMe₂Ge-Cp)(NtBu₂)₃,Zr(FMe₂Ge-Cp)(NHtBu)₃, Zr((CF₃)₃Ge-Cp)(NMe₂)₃, Zr((CF₃)₃Ge-Cp)(NHMe)₃,Zr((CF₃)₃Ge-Cp)(NEt₂)₃, Zr((CF₃)₃Ge-Cp)(NHEt)₃, Zr((CF₃)₃Ge-Cp)(NEtMe)₃,Zr((CF₃)₃Ge-Cp)(NnPr₂)₃, Zr((CF₃)₃Ge-Cp)(NHnPr)₃,Zr((CF₃)₃Ge-Cp)(NiPr₂)₃, Zr((CF₃)₃Ge-Cp)(NHiPr)₃,Zr((CF₃)₃Ge-Cp)(NnBu₂)₃, Zr((CF₃)₃Ge-Cp)(NHnBu)₃,Zr((CF₃)₃Ge-Cp)(NiBu₂)₃, Zr((CF₃)₃Ge-Cp)(NHiBu)₃,Zr((CF₃)₃Ge-Cp)(NsBu₂)₃, Zr((CF₃)₃Ge-Cp)(NHsBu)₃,Zr((CF₃)₃Ge-Cp)(NtBu₂)₃, Zr((CF₃)₃Ge-Cp)(NHtBu)₃,Zr((CF₃)₂HGe-Cp)(NMe)₃, Zr((CF₃)₂HGe-Cp)(NHMe)₃,Zr((CF₃)₂HGe-Cp)(NEt₂)₃, Zr((CF₃)₂HGe-Cp)(NHEt)₃,Zr((CF₃)₂HGe-Cp)(NEtMe)₃, Zr((CF₃)₂HGe-Cp)(NnPr₂)₃,Zr((CF₃)₂HGe-Cp)(NHnPr)₃, Zr((CF₃)₂HGe-Cp)(NiPr₂)₃,Zr((CF₃)₂HGe-Cp)(NHiPr)₃, Zr((CF₃)₂HGe-Cp)(NnBu₂)₃,Zr((CF₃)₂HGe-Cp)(NHnBu)₃, Zr((CF₃)₂HGe-Cp)(NiBu₂)₃,Zr((CF₃)₂HGe-Cp)(NHiBu)₃, Zr((CF₃)₂HGe-Cp)(NsBu₂)₃,Zr((CF₃)₂HGe-Cp)(NHsBu)₃, Zr((CF₃)₂HGe-Cp)(NtBu₂)₃,Zr((CF₃)₂HGe-Cp)(NHtBu)₃, Zr((CF₃)Me₂Ge-Cp)(NMe₂)₃,Zr((CF₃)Me₂Ge-Cp)(NHMe)₃, Zr((CF₃)Me₂Ge-Cp)(NEt₂)₃,Zr((CF₃)Me₂Ge-Cp)(NHEt)₃, Zr((CF₃)Me₂Ge-Cp)(NEtMe)₃,Zr((CF₃)Me₂Ge-Cp)(NnPr₂)₃, Zr((CF₃)Me₂Ge-Cp)(NHnPr)₃,Zr((CF₃)Me₂Ge-Cp)(NiPr₂)₃, Zr((CF₃)Me₂Ge-Cp)(NHiPr)₃,Zr((CF₃)Me₂Ge-Cp)(NnBu₂)₃, Zr((CF₃)Me₂Ge-Cp)(NHnBu)₃,Zr((CF₃)Me₂Ge-Cp)(NiBu₂)₃, Zr((CF₃)Me₂Ge-Cp)(NHiBu)₃,Zr((CF₃)Me₂Ge-Cp)(NsBu₂)₃, Zr((CF₃)Me₂Ge-Cp)(NHsBu)₃,Zr((CF₃)Me₂Ge-Cp)(NtBu₂)₃, or Zr((CF₃)Me₂Ge-Cp)(NHtBu)₃.

Exemplary Germanium- and Zirconium-containing precursors of Formula IIinclude but are not limited to Zr(TMG-Cp)(OMe)₃, Zr(TMG-Cp)(OEt)₃,Zr(TMG-Cp)(OnPr)₃, Zr(TMG-Cp)(OiPr)₃, Zr(TMG-Cp)(OtBu)₃,Zr(TMG-Cp)(OsBu)₃, Zr(TMG-Cp)(OnBu)₃, Zr(TMG-Cp)(OiBu)₃,Zr(DMG-Cp)(OMe)₃, Zr(DMG-Cp)(OEt)₃, Zr(DMG-Cp)(OnPr)₃,Zr(DMG-Cp)(OiPr)₃, Zr(DMG-Cp)(OtBu)₃, Zr(DMG-Cp)(OsBu)₃,Zr(DMG-Cp)(OnBu)₃, Zr(DMG-Cp)(OiBu)₃, Zr(F₃Ge-Cp)(OMe)₃,Zr(F₃Ge-Cp)(OEt)₃, Zr(F₃Ge-Cp)(OnPr)₃, Zr(F₃Ge-Cp)(OiPr)₃,Zr(F₃Ge-Cp)(OtBu)₃, Zr(F₃Ge-Cp)(OsBu)₃, Zr(F₃Ge-Cp)(OnBu)₃,Zr(F₃Ge-Cp)(OiBu)₃, Zr(F₂HGe-Cp)(OMe)₃, Zr(F₂HGe-Cp)(OEt)₃,Zr(F₂HGe-Cp)(OnPr)₃, Zr(F₂HGe-Cp)(OiPr)₃, Zr(F₂HGe-Cp)(OtBu)₃,Zr(F₂HGe-Cp)(OsBu)₃, Zr(F₂HGe-Cp)(OnBu)₃, Zr(F₂HGe-Cp)(OiBu)₃,Zr(FH₂Ge-Cp)(OMe)₃, Zr(FH₂Ge-Cp)(OEt)₃, Zr(FH₂Ge-Cp)(OnPr)₃,Zr(FH₂Ge-Cp)(OiPr)₃, Zr(FH₂Ge-Cp)(OtBu)₃, Zr(FH₂Ge-Cp)(OsBu)₃,Zr(FH₂Ge-Cp)(OnBu)₃, Zr(FH₂Ge-Cp)(OiBu)₃, Zr(FMe₂Ge-Cp)(OMe)₃,Zr(FMe₂Ge-Cp)(OEt)₃, Zr(FMe₂Ge-Cp)(OnPr)₃, Zr(FMe₂Ge-Cp)(OiPr)₃,Zr(FMe₂Ge-Cp)(OtBu)₃, Zr(FMe₂Ge-Cp)(OsBu)₃, Zr(FMe₂Ge-Cp)(OnBu)₃,Zr(FMe₂Ge-Cp)(OiBu)₃, Zr((CF₃)₃Ge-Cp)(OMe)₃, Zr((CF₃)₃Ge-Cp)(OEt)₃,Zr((CF₃)₃Ge-Cp)(OnPr)₃, Zr((CF₃)₃Ge-Cp)(OiPr)₃, Zr((CF₃)₃Ge-Cp)(OtBu)₃,Zr((CF₃)₃Ge-Cp)(OsBu)₃, Zr((CF₃)₃Ge-Cp)(OnBu)₃, Zr((CF₃)₃Ge-Cp)(OiBu)₃,Zr((CF₃)₂HGe-Cp)(OMe)₃, Zr((CF₃)₂HGe-Cp)(OEt)₃, Zr((CF₃)₂HGe-Cp)(OnPr)₃,Zr((CF₃)₂HGe-Cp)(OiPr)₃, Zr((CF₃)₂HGe-Cp)(OtBu)₃,Zr((CF₃)₂HGe-Cp)(OsBu)₃, Zr((CF₃)₂HGe-Cp)(OnBu)₃,Zr((CF₃)₂HGe-Cp)(OiBu)₃, Zr((CF₃)Me₂Ge-Cp)(OMe)₃,Zr((CF₃)Me₂Ge-Cp)(OEt)₃, Zr((CF₃)Me₂Ge-Cp)(OnPr)₃,Zr((CF₃)Me₂Ge-Cp)(OiPr)₃, Zr((CF₃)Me₂Ge-Cp)(OtBu)₃,Zr((CF₃)Me₂Ge-Cp)(OsBu)₃, Zr((CF₃)Me₂Ge-Cp)(OnBu)₃, orZr((CF₃)Me₂Ge-Cp)(OiBu)₃.

Preferably, the Germanium- and Zirconium-containing precursor is(trimethylgermyl)cyclopentadienyl tris(dimethylamino)Zirconium(IV), dueto its vaporization results in atmospheric thermo gravimetric analysis,leaving a small amount of final residue (see Example 1).

The disclosed Germanium- and Zirconium-film forming compositions may besynthesized by reacting the corresponding tetrakis(amino)Zirconium(IV)or corresponding tetrakis(alkoxy) Zirconium(IV) with the corresponding(germyl)cyclopentadiene in a suitable solvent, such as toluene, THF orether. (Germyl)cyclopentadiene are typically prepared according to theprocedure described in Organometallics 1990, 9, 2488-2492. Alternativelythe disclosed (germyl)cyclopentadienyl-tris(alkoxy)Zirconium-containingcompounds may be synthesized by alcoholysis of the corresponding(germyl)cyclopentadienyl-tris(amino)Zirconium-containing compounds with3 equivalents of the corresponding alcohol in a suitable solvent, suchas toluene, THF or ether. Exemplary synthesis method containing furtherdetails are provided in the Examples that follow.

Purity of the disclosed Germanium- and Zirconium-film formingcompositions is higher than 95% w/w, preferably higher than 98% w/w, andmore preferably higher than 99% w/w. One of ordinary skill in the artwill recognize that the purity may be determined by H NMR or gas orliquid chromatography with mass spectrometry. The disclosed Germanium-and Zirconium-film forming compositions may contain any of the followingimpurities: cyclopentadiene; (germyl)cyclopentadiene; dicyclopentadiene;alkylgermane; alkylamines such as tertbutylamine; dialkylamines such asdimethylamine; alkylimines; alcohol such as isopropylalcohol ortertbutylalcohol; THF; ether; pentane; cyclohexane; heptanes; toluene;chlorinated metal compounds; lithium, sodium or potassium alkoxy;lithium, sodium, or potassium alkylamino; or lithium, sodium, orpotassium cyclopentadienyl. The total quantity of these impurities isbelow 5% w/w, preferably below 2% w/w, and more preferably below 1% w/w.The composition may be purified by recrystallisation, sublimation,distillation, and/or passing the gas or liquid through a suitableadsorbent, such as a 4A molecular sieve.

Purification of the disclosed Germanium- and Zirconium-film formingcompositions may also result in metal impurities at the 0 ppbw (partsper billion weight) to 1 ppmw (parts per million weight) levels,preferably 0-500 ppbw level. These metal impurities include, but are notlimited to, Aluminum (Al), Arsenic (As), Barium (Ba), Beryllium (Be),Bismuth (Bi), Cadmium (Cd), Calcium (Ca), Chromium (Cr), Cobalt (Co),Copper (Cu), Gallium (Ga), Germanium (Ge), Hafnium (Hf), Zirconium (Zr),Indium (In), Iron (Fe), Lead (Pb), Lithium (Li), Magnesium (Mg),Manganese (Mn), Tungsten (W), Nickel (Ni), Potassium (K), Sodium (Na),Strontium (Sr), Thorium (Th), Tin (Sn), Titanium (Ti), Uranium (U),Vanadium (V) and Zinc (Zn).

Also disclosed are methods for forming Zirconium-containing layers on asubstrate using a vapor deposition process. The method may be useful inthe manufacture of semiconductor, photovoltaic, LCD-TFT, or flat paneltype devices. The disclosed Germanium- and Zirconium-film formingcompositions may be used to deposit thin Zirconium-containing filmsusing any deposition methods known to those of skill in the art.

Examples of suitable deposition methods include, without limitation,chemical vapor deposition (CVD) or atomic layer deposition (ALD).Exemplary CVD methods include thermal CVD, plasma enhanced CVD (PECVD),pulsed CVD (PCVD), low pressure CVD (LPCVD), sub-atmospheric CVD(SACVD), atmospheric pressure CVD (APCVD), hot-wire CVD (HWCVD, alsoknown as cat-CVD, in which a hot wire serves as an energy source for thedeposition process), radicals incorporated CVD, and combinationsthereof. Exemplary ALD methods include thermal ALD, plasma enhanced ALD(PEALD), spatial isolation ALD, hot-wire ALD (HWALD), radicalsincorporated ALD, and combinations thereof. Super critical fluiddeposition may also be used. The deposition method is preferably ALD,PE-ALD, or spatial ALD in order to provide suitable step coverage andfilm thickness control.

The cubic/tetragonal crystalline phase of ZrO₂ provides the highestdielectric constant of the different ZrO₂ crystalline forms (cubic,tetragonal, amorphous, monoclinic, orthorhombic, and combinationsthereof are the available crystalline phases). It is experimentallyreported that a doping level (3-12%) of small ionic radius tetravalentdopant such as Ge is the most efficient in stabilizing the tetragonalzirconia phase. The substitution of a Zr atom by Ge in the tetragonalZrO₂ structure results in reduced Ge—O bond with length similar to thatin GeO₂. Therefore, ZrO₂ is an excellent host for Ge, which is easilyincorporated into the “friendly” local environment of the oxide (J.Appl. Phys. 106, 024107, 2009). The advantage is that Ge is tetravalenttherefore it substitutes Zr in the lattice without introducing Ovacancies.

Applicants believe that the vapor deposition process conditions may becontrolled so that Zr alone or both Zr and Ge may be deposited in thezirconium-containing layer. For instance, adjusting the ALD parametersto exhibit some parasitic CVD might be useful to deposit a finite amountof Ge in the ZrO₂ layer. Alternatively, the germanium content in ZrO₂film may be controlled by alternating the deposition of (Zr, Ge)O₂ filmusing the disclosed Germanium- and Zirconium-film forming compositionsand the deposition of pure ZrO₂ using another zirconium-containingprecursor. For example, ZrCp(NMe₂)₃, Zr(MeCp)(NMe₂)₃ or Zr(EtCp)(NMe₂)₃may serve as the Zr-containing precursor to produce pure ZrO₂ films. Inother words x subcycles of (Zr, Ge)O₂ deposition using the Germanium-and Zirconium-film forming compositions may be alternated with ysubcycles of pure ZrO₂ deposition using a zirconium-containingprecursor, such as ZrCp(NMe₂)₃. The supercycle consisting of x subcyclesof (Zr, Ge)O₂ and y subcycles of pure ZrO₂ may be repeated to obtain adesired thickness of (Zr, Ge)O₂ film, wherein x and y are integers whichinclusively range from 1 to 20. Zr and Ge content may be controlled byadjusting x and y.

Alternatively, the germanium content in the ZrO₂ film may be controlledby depositing the (Zr, Ge)O₂ film using a mixture containing both thedisclosed Germanium- and Zirconium-film forming compositions and azirconium-containing precursor. For example, ZrCp(NMe₂)₃,Zr(MeCp)(NMe₂)₃, Zr(EtCp)(NMe₂)₃, Zr(iPrCp)(NMe₂)₃, or Zr(tBuCp)(NMe₂)₃may serve as the Zr-containing precursor. The Zr and Ge content may becontrolled by adjusting the ratio between the Germanium- andZirconium-film forming composition and the zirconium-containingprecursor in the mixture.

The disclosed Germanium- and Zirconium-film forming compositions may besupplied either in neat form or in a blend with a suitable solvent, suchas ethyl benzene, xylene, mesitylene, decane, or dodecane. The disclosedcompositions may be present in varying concentrations in the solvent.

The neat or blended Germanium- and Zirconium-film forming compositionsare introduced into a reactor in vapor form by conventional means, suchas tubing and/or flow meters. The composition in vapor form may beproduced by vaporizing the neat or blended composition through aconventional vaporization step such as direct vaporization,distillation, direct liquid injection, by bubbling, or by using asublimator such as the one disclosed in PCT Publication WO2009/087609 toXu et al. The neat or blended composition may be fed in liquid state toa vaporizer where it is vaporized before it is introduced into thereactor. Alternatively, the neat or blended composition may be vaporizedby passing a carrier gas into a container containing the compound or bybubbling the carrier gas into the composition. The carrier gas mayinclude, but is not limited to, Ar, He, N₂, and mixtures thereof.Bubbling with a carrier gas may also remove any dissolved oxygen presentin the neat or blended composition. The carrier gas and composition arethen introduced into the reactor as a vapor.

If necessary, the container of disclosed composition may be heated to atemperature that permits the compound to be in its liquid phase and tohave a sufficient vapor pressure. The container may be maintained attemperatures in the range of, for example, approximately 0° C. toapproximately 150° C. Those skilled in the art recognize that thetemperature of the container may be adjusted in a known manner tocontrol the amount of precursor vaporized.

The reactor may be any enclosure or chamber within a device in whichdeposition methods take place such as without limitation, aparallel-plate type reactor, a cold-wall type reactor, a hot-wall typereactor, a single-wafer reactor, a multi-wafer reactor, or other typesof deposition systems under conditions suitable to cause the compoundsto react and form the layers.

Generally, the reactor contains the substrate(s) onto which the thinfilms will be deposited. A substrate is generally defined as thematerial on which a process is conducted. The substrates may be anysuitable substrate used in semiconductor, photovoltaic, flat panel, orLCD-TFT device manufacturing. Examples of suitable substrates includewafers, such as silicon, silica, glass, or GaAs wafers. The wafer mayhave one or more layers of differing materials deposited on it from aprevious manufacturing step. For example, the wafers may include siliconlayers (crystalline, amorphous, porous, etc.), silicon oxide layers,silicon nitride layers, silicon oxy nitride layers, carbon doped siliconoxide (SiCOH) layers, or combination thereof. Additionally, the wafersmay include copper layers, tungsten layers, or noble metal layers (e.g.,platinum, palladium rhodium, or gold). Plastic layers, such aspoly(3,4-ethylenedioxythiophene)poly (styrenesulfonate) [PEDOT:PSS], mayalso be used. The layers may be planar or patterned. The disclosedprocesses may deposit the Zr-containing layer directly on the wafer ordirectly on one or more than one (when patterned layers from thesubstrate) of the layers on top of the wafer. Furthermore, one ofordinary skill in the art will recognize that the terms “film” or“layer” used herein refer to a thickness of some material laid on orspread over a surface and that the surface may be a trench or a line.Throughout the specification and claims, the wafer and any associatedlayers thereon are referred to as substrates. For example, a ZrO₂ filmmay be deposited onto a TiN substrate. In subsequent processing, a TiNlayer may be deposited on the ZrO₂ layer, forming a TiN/ZrO₂/TiN stackused as DRAM capacitor.

The temperature and the pressure within the reactor are held atconditions suitable for vapor depositions. In other words, afterintroduction of the vaporized composition into the chamber, conditionswithin the chamber are such that at least part of the vaporizedprecursor is deposited onto the substrate to form a Zirconium-containingfilm. For instance, the pressure in the reactor may be held betweenabout 1 Pa and about 10⁵ Pa, more preferably between about 25 Pa andabout 10³ Pa, as required per the deposition parameters. Likewise, thetemperature in the reactor may be held between about 100° C. and about500° C., preferably between about 150° C. and about 400° C. One ofordinary skill in the art will recognize that “at least part of thevaporized precursor is deposited” means that some or all of theprecursor reacts with or adheres to the substrate.

The temperature of the reactor may be controlled by either controllingthe temperature of the substrate holder or controlling the temperatureof the reactor wall. Devices used to heat the substrate are known in theart. The reactor wall is heated to a sufficient temperature to obtainthe desired film at a sufficient growth rate and with desired physicalstate and composition. A non-limiting exemplary temperature range towhich the reactor wall may be heated includes from approximately 100° C.to approximately 500° C. When a plasma deposition process is utilized,the deposition temperature may range from approximately 150° C. toapproximately 400° C. Alternatively, when a thermal process isperformed, the deposition temperature may range from approximately 200°C. to approximately 500° C.

In addition to the disclosed compound, a reactant may also be introducedinto the reactor. The reactant may be an oxidizing gas such as one ofO₂, O₃, H₂O, H₂O₂, NO, N₂O, NO₂, oxygen-containing radicals such as O.or OH., NO, NO₂, carboxylic acids, formic acid, acetic acid, propionicacid, and mixtures thereof. Preferably, the oxidizing gas is selectedfrom the group consisting of O₂, O₃, H₂O, H₂O₂, oxygen-containingradicals thereof such as O. or OH., and mixtures thereof.

Alternatively, the reactant may be a reducing gas such as one of H₂,H₂CO, NH₃, SiH₄, Si₂H₆, Si₃H₈, (CH₃)₂SiH₂, (C₂H₅)₂SiH₂, (CH₃)SiH₃,(C₂H₅)SiH₃, phenyl silane, N₂H₄, N(SiH₃)₃, N(CH₃)H₂, N(C₂H₅)H₂,N(CH₃)₂H, N(C₂H₅)₂H, N(CH₃)₃, N(C₂H₅)₃, (SiMe₃)₂NH, (CH₃)HNNH₂,(CH₃)₂NNH₂, phenyl hydrazine, N-containing molecules, B₂H₆,9-borabicyclo[3,3,1]nonane, dihydrobenzenfuran, pyrazoline,trimethylaluminium, dimethylzinc, diethylzinc, radical species thereof,and mixtures thereof. Preferably, the reducing as is H₂, NH₃, SiH₄,Si₂H₆, Si₃H₈, SiH₂Me₂, SiH₂Et₂, N(SiH₃)₃, hydrogen radicals thereof, ormixtures thereof.

The reactant may be treated by plasma, in order to decompose thereactant into its radical form. N₂ may also be utilized as a reducinggas when treated with plasma. For instance, the plasma may be generatedwith a power ranging from about 50 W to about 500 W, preferably fromabout 100 W to about 400 W. The plasma may be generated or presentwithin the reactor itself. Alternatively, the plasma may generally be ata location removed from the reactor, for instance, in a remotely locatedplasma system. One of skill in the art will recognize methods andapparatus suitable for such plasma treatment.

For example, the reactant may be introduced into a direct plasmareactor, which generates plasma in the reaction chamber, to produce theplasma-treated reactant in the reaction chamber. Exemplary direct plasmareactors include the Titan™ PECVD System produced by Trion Technologies.The reactant may be introduced and held in the reaction chamber prior toplasma processing. Alternatively, the plasma processing may occursimultaneously with the introduction of the reactant. In-situ plasma istypically a 13.56 MHz RF inductively coupled plasma that is generatedbetween the showerhead and the substrate holder. The substrate or theshowerhead may be the powered electrode depending on whether positiveion impact occurs. Typical applied powers in in-situ plasma generatorsare from approximately 30 W to approximately 1000 W. Preferably, powersfrom approximately 30 W to approximately 600 W are used in the disclosedmethods. More preferably, the powers range from approximately 100 W toapproximately 500 W. The disassociation of the reactant using in-situplasma is typically less than achieved using a remote plasma source forthe same power input and is therefore not as efficient in reactantdisassociation as a remote plasma system, which may be beneficial forthe deposition of Zirconium-containing films on substrates easilydamaged by plasma.

Alternatively, the plasma-treated reactant may be produced outside ofthe reaction chamber. The MKS Instruments' ASTRONi® reactive gasgenerator may be used to treat the reactant prior to passage into thereaction chamber. Operated at 2.45 GHz, 7 kW plasma power, and apressure ranging from approximately 0.5 Torr to approximately 10 Torr,the reactant O₂ may be decomposed into two O. radicals. Preferably, theremote plasma may be generated with a power ranging from about 1 kW toabout 10 kW, more preferably from about 2.5 kW to about 7.5 kW.

The vapor deposition conditions within the chamber allow the disclosedprecursors and the reactant to react and form a Zirconium-containingfilm on the substrate. In some embodiments, Applicants believe thatplasma-treating the reactant may provide the reactant with the energyneeded to react with the disclosed precursor.

Depending on what type of film is desired to be deposited, an additionalprecursor compound may be introduced into the reactor. The additionalprecursor may be used to provide the same (i.e., Zr) or additionalelements to the Zirconium-containing film. The additional elements mayinclude Hafnium, Niobium, Tantalum, lanthanides (Ytterbium, Erbium,Dysprosium, Gadolinium, Praseodymium, Cerium, Lanthanum, Yttrium),germanium, silicon, titanium, manganese, cobalt, nickel, ruthenium,bismuth, lead, magnesium, aluminum, or mixtures of these. When anadditional precursor compound is utilized, the resultant film depositedon the substrate may contain the Zirconium in combination with at leastone additional element.

The Germanium- and Zirconium-film forming compositions and reactants maybe introduced into the reactor either simultaneously (chemical vapordeposition), sequentially (atomic layer deposition), or differentcombinations thereof. The reactor may be purged with an inert gasbetween the introduction of the composition and the introduction of thereactant. Alternatively, the reactant and the composition may be mixedtogether to form a reactant/composition mixture, and then introduced tothe reactor in mixture form. Another example is to introduce thereactant continuously and to introduce the Germanium- and Zirconium-filmforming composition by pulse (pulsed chemical vapor deposition).

The vaporized composition and the reactant may be pulsed sequentially orsimultaneously (e.g. pulsed CVD) into the reactor. Each pulse ofcomposition may last for a time period ranging from about 0.01 secondsto about 10 seconds, alternatively from about 0.3 seconds to about 3seconds, alternatively from about 0.5 seconds to about 2 seconds. Inanother embodiment, the reactant may also be pulsed into the reactor. Insuch embodiments, the pulse of each gas may last for a time periodranging from about 0.01 seconds to about 10 seconds, alternatively fromabout 0.3 seconds to about 3 seconds, alternatively from about 0.5seconds to about 2 seconds. In another alternative, the vaporizedcomposition and one or more reactants may be simultaneously sprayed froma shower head under which a susceptor holding several wafers is spun(spatial ALD).

Depending on the particular process parameters, deposition may takeplace for a varying length of time. Generally, deposition may be allowedto continue as long as desired or necessary to produce a film with thenecessary properties. Typical film thicknesses may vary from severalangstroms to several hundreds of microns, depending on the specificdeposition process. The deposition process may also be performed as manytimes as necessary to obtain the desired film thickness.

In one non-limiting exemplary CVD type process, the vapor phase of thedisclosed Germanium- and Zirconium-film forming composition and areactant are simultaneously introduced into the reactor. The two reactto form the resulting Zirconium-containing thin film. When the reactantin this exemplary CVD process is treated with plasma, the exemplary CVDprocess becomes an exemplary PECVD process. The reactant may be treatedwith plasma prior or subsequent to introduction into the chamber.

In one non-limiting exemplary ALD type process, the vapor phase of thedisclosed Germanium- and Zirconium-film forming composition isintroduced into the reactor, where it is contacted with a suitablesubstrate. Excess composition may then be removed from the reactor bypurging and/or evacuating the reactor. A desired gas (for example, H₂)is introduced into the reactor where it reacts with the absorbedcomposition in a self-limiting manner. Any excess reducing gas isremoved from the reactor by purging and/or evacuating the reactor. Ifthe desired film is a Zirconium film, this two-step process may providethe desired film thickness or may be repeated until a film having thenecessary thickness has been obtained.

Alternatively, if the desired film contains Zirconium and a secondelement, the two-step process above may be followed by introduction ofthe vapor of an additional precursor compound into the reactor. Theadditional precursor compound will be selected based on the nature ofthe Zirconium film being deposited. After introduction into the reactor,the additional precursor compound is contacted with the substrate. Anyexcess precursor compound is removed from the reactor by purging and/orevacuating the reactor. Once again, a desired gas may be introduced intothe reactor to react with the precursor compound. Excess gas is removedfrom the reactor by purging and/or evacuating the reactor. If a desiredfilm thickness has been achieved, the process may be terminated.However, if a thicker film is desired, the entire four-step process maybe repeated. By alternating the provision of the Germanium- andZirconium-film forming composition, additional precursor compound, andreactant, a film of desired composition and thickness can be deposited.

When the reactant in this exemplary ALD process is treated with plasma,the exemplary ALD process becomes an exemplary PEALD process. Thereactant may be treated with plasma prior or subsequent to introductioninto the chamber.

In a second non-limiting exemplary ALD type process, the vapor phase ofone of the disclosed Ge- and Zr-film forming compositions, for example(trimethylgermyl)cyclopentadienyl tris(dimethylamino) Zirconium(IV), isintroduced into the reactor, where it is contacted with a TiN substrate.Excess Ge- and Zr-film forming composition may then be removed from thereactor by purging and/or evacuating the reactor. A desired gas (forexample, O₃) is introduced into the reactor where it reacts with theabsorbed Ge- and Zr-film forming composition in a self-limiting mannerto form a ZrO₂ or (Zr, Ge)O₂ film. Any excess oxidizing gas is removedfrom the reactor by purging and/or evacuating the reactor. These twosteps may be repeated until the ZrO₂ or (Zr, Ge)O₂ film obtains adesired thickness. A TiN layer may then be deposited on top of the ZrO₂or (Zr, Ge)O₂ layer. The resulting TiN/ZrO₂/TiN or TiN/(Zr, Ge)O₂/TiNstack may be used in DRAM capacitors.

In a third non-limiting exemplary ALD type process, the vapor phase ofone of the disclosed Ge- and Zr-film forming compositions, for example(trimethylgermyl)cyclopentadienyl tris(dimethylamino)Zirconium(IV), isintroduced in a first step into the reactor, where it is contacted witha TiN substrate. Excess Ge- and Zr-film forming composition may then beremoved from the reactor by purging and/or evacuating the reactor. Adesired gas (for example, O₃) is introduced into the reactor where itreacts with the absorbed Ge- and Zr-containing precursor in aself-limiting manner to form a (Zr, Ge)O₂ film. Any excess oxidizing gasis removed from the reactor by purging and/or evacuating the reactor.These two steps may be considered as a subcycle and may be repeated xtimes to obtain a desired thickness of the (Zr, Ge)O₂ film. In a secondstep the vapor phase of a Zr-containing precursor, for example(methyl)cyclopentadienyl tris(dimethylamino)Zirconium(IV) or(ethyl)cyclopentadienyl tris(dimethylamino)Zirconium(IV) is introducedinto the same reactor. Excess Zr-containing precursor may then beremoved from the reactor by purging and/or evacuating the reactor. Adesired gas (for example, O₃) is introduced into the reactor where itreacts with the Zr-containing precursor in a self-limiting manner toform a ZrO₂ film. Any excess oxidizing gas is removed from the reactorby purging and/or evacuating the reactor. These two steps may beconsidered as a subcycle and may be repeated y times to obtain a desiredthickness of pure ZrO₂ film. The supercycle consisting of x subcycles of(Zr, Ge)O₂ and y subcycles of pure ZrO₂ may be be repeated to obtain adesired thickness of (Zr, Ge)O₂ film. Zr and Ge content may becontrolled by adjusting the number of x and y cycles (x and y mayindependently range from 1 to 20). A TiN layer may then be deposited ontop of the ZrO₂ or (Zr, Ge)O₂ layer. The resulting TiN/ZrO₂/TiN orTiN/(Zr, Ge)O₂/TiN stack may be used in DRAM capacitors.

In a fourth non-limiting exemplary ALD type process, the vapor phase ofa mixture containing the disclosed Ge- and Zr-film forming composition,for example (trimethylgermyl)cyclopentadienyltris(dimethylamino)Zirconium(IV), and a Zr-containing precursor, forexample (isopropyl)cyclopentadienyl tris(dimethylamino)Zirconium(IV) or(tertbutyl)cyclopentadienyl tris(dimethylamino)Zirconium(IV), isintroduced into the reactor, where it is contacted with a substrate, forexample TiN, NbN, Ru, TiO₂, MoO₂ or MoO₃. Excess mixture may then beremoved from the reactor by purging and/or evacuating the reactor. Adesired gas (for example, O₃) is introduced into the reactor where itreacts with the absorbed mixture in a self-limiting manner to form a(Zr, Ge)O₂ film. Any excess oxidizing gas is removed from the reactor bypurging and/or evacuating the reactor. These two steps may be repeateduntil the (Zr, Ge)O₂ film obtains a desired thickness. The Zr and Gecontent may be controlled by adjusting the ratio between the Germanium-and Zirconium-film forming composition and the zirconium-containingprecursor in the mixture. A TiN layer may be deposited on top of the(Zr, Ge)O₂ layer. The resulting TiN/ZrO₂/TiN or TiN/(Zr, Ge)O₂/TiN stackmay be used in DRAM capacitors.

The Zirconium-containing films resulting from the processes discussedabove may include a pure Zirconium, Zirconium silicide (Zr_(k)Si_(i)),Zirconium oxide (Zr_(m)O_(n)), Germanium-doped Zirconium oxide(Zr_(r)Ge_(s)O_(t)), Zirconium nitride (ZOO, or germanium-doped siliconnitride (Zr_(t)Ge_(u)N_(v)), wherein k, l, m, n, o, p, q, r, s, t, u andv are integers which inclusively range from 1 to 6. One of ordinaryskill in the art will recognize that by judicial selection of theappropriate disclosed compound, optional precursor compounds, andreactant species, the desired film composition may be obtained.

Upon obtaining a desired film thickness, the film may be subject tofurther processing, such as thermal annealing, furnace-annealing, rapidthermal annealing, UV or e-beam curing, and/or plasma gas exposure.Those skilled in the art recognize the systems and methods utilized toperform these additional processing steps. For example, theZirconium-containing film may be exposed to a temperature ranging fromapproximately 200° C. and approximately 1000° C. for a time ranging fromapproximately 0.1 second to approximately 7200 seconds under an inertatmosphere, a H-containing atmosphere, a N-containing atmosphere, anO-containing atmosphere, or combinations thereof. Most preferably, thetemperature is 400° C. for 3600 seconds under a H-containing atmosphereor an O-containing atmosphere. The resulting film may contain fewerimpurities and therefore may have an improved density resulting inimproved leakage current. The annealing step may be performed in thesame reaction chamber in which the deposition process is performed.Alternatively, the substrate may be removed from the reaction chamber,with the annealing/flash annealing process being performed in a separateapparatus. Any of the above post-treatment methods, but especiallythermal annealing, has been found effective to reduce carbon andnitrogen contamination of the Zirconium-containing film. This in turntends to improve the resistivity of the film.

EXAMPLES

The following examples illustrate experiments performed in conjunctionwith the disclosure herein. The examples are not intended to be allinclusive and are not intended to limit the scope of disclosuredescribed herein.

Example 1 (trimethylgermyl)cyclopentadienyl tris(dimethylamino)Zirconium(IV) synthesis [Zr(TMG-Cp)(NMe₂)₃]

To a solution of Zr(NMe₂)₄ (1.33 g, 0.005 mol) in ca. 20 mL of tolueneat room temperature, was added dropwise a freshly distillated TMGCpH(0.93 g, 0.005 mol). The mixture was stirred overnight. Solvent was thenremoved under vacuum to give yellow oil. The material was then purifiedby distillation at 120° C.@6 mTorr to give 1.38 g (68%) of pure yellowoil. The NMR¹H spectrum is provided in FIG. 1. NMR¹H (δ, ppm, C6D6):6.28 (t, 2H), 6.23 (t, 2H), 2.95 (s, 18H), 0.38 (s, 9H).

The oil left a 3.9% residual mass during TGA analysis measured at atemperature rising rate of 10° C./min in an atmosphere which flowsnitrogen at 200 mL/min. These results are shown in FIG. 3, which is aTGA/DTA graph illustrating the percentage of weight loss (TGA) anddifferential temperature (DTA) upon temperature increase.

Example 2 (trimethylgermyl)cyclopentadienyl tris(isopropoxy)Zirconium(IV) synthesis [Zr(TMG-Cp)(OiPr)₃]

To a solution of Zr(TMGCp)(NMe₂)₃ (1.26 g, 2.8 mmol) in ca. 20 mL ofTHF, was added drop wise anhydrous isopropanol (0.63 g, 10.5 mmol). Themixture was stirred overnight at room temperature. Solvent was thenremoved under vacuum to give bright yellow oil. The material was thenpurified by distillation at 90° C.@20 mTorr to give 0.39 g (31%) of pureslightly yellow oil. The NMR¹H spectrum is provided in FIG. 2. NMR¹H (δ,ppm, C6D6): 6.56 (t, 2H), 6.43 (t, 2H), 4.25 (m, 3H), 1.17 (d, 18H),0.48 (s, 9H).

The oil left a 1.6% residual mass during TGA analysis measured at atemperature rising rate of 10° C./min in an atmosphere which flowsnitrogen at 200 mL/min. These results are shown in FIG. 4, which is aTGA/DTA graph illustrating the percentage of weight loss (TGA) anddifferential temperature (DTA) upon temperature increase.

It will be understood that many additional changes in the details,materials, steps, and arrangement of parts, which have been hereindescribed and illustrated in order to explain the nature of theinvention, may be made by those skilled in the art within the principleand scope of the invention as expressed in the appended claims. Thus,the present invention is not intended to be limited to the specificembodiments in the examples given above and/or the attached drawings.

We claim:
 1. A Germanium- and Zirconium-film forming compositioncomprising a precursor having one of the following formulae:

wherein each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹ and R¹⁰ is independentlyselected from the group consisting of H; a C1-C5 linear, branched, orcyclic alkyl group; and a C1-C5 linear, branched, or cyclic fluoroalkylgroup.
 2. The Germanium- and Zirconium-film forming composition of claim1, having the Formula I:


3. The Germanium- and Zirconium-film forming composition of claim 2,wherein the precursor is selected from the group consisting of:(trimethylgermyl)cyclopentadienyl tris(Dimethylamino)Zirconium(IV)(Zr(TMG-Cp)(NMe₂)₃); (trimethylgermyl)cyclopentadienyl tris(methylamino)Zirconium(IV) (Zr(TMG-Cp)(NHMe)₃); (trimethylgermyl)cyclopentadienyltris(Diethylamino)Zirconium(IV) (Zr(TMG-Cp)(NEt₂)₃);(trimethylgermyl)cyclopentadienyl tris(ethylamino)Zirconium(IV)(Zr(TMG-Cp)(NHEt)₃); (trimethylgermyl)cyclopentadienyltris(ethylmethylamino) Zirconium(IV) (Zr(TMG-Cp)(NEtMe)₃);(trimethylgermyl)cyclopentadienyl tris(Di n-propylamino)Zirconium(IV)(Zr(TMG-Cp)(NnPr₂)₃); (trimethylgermyl)cyclopentadienyltris(n-propylamino)Zirconium(IV) (Zr(TMG-Cp)(NHnPr)₃);(trimethylgermyl)cyclopentadienyl tris(Di isopropylamino)Zirconium(IV)(Zr(TMG-Cp)(NiPr₂)₃); (trimethylgermyl)cyclopentadienyltris(isopropylamino)Zirconium(IV) (Zr(TMG-Cp)(NH iPr)₃);(trimethylgermyl)cyclopentadienyl tris(Di n-butylamino)Zirconium(IV)(Zr(TMG-Cp)(NnBu₂)₃); (trimethylgermyl)cyclopentadienyltris(n-butylamino)Zirconium(IV) (Zr(TMG-Cp)(NHnBu)₃)(trimethylgermyl)cyclopentadienyl tris(Di isobutylamino)Zirconium(IV)(Zr(TMG-Cp)(NiBu₂)₃); (trimethylgermyl)cyclopentadienyltris(isobutylamino)Zirconium(IV) (Zr(TMG-Cp)(NHiBu)₃);(trimethylgermyl)cyclopentadienyl tris(Di sec-butylamino)Zirconium(IV)(Zr(TMG-Cp)(NsBu₂)₃); (trimethylgermyl)cyclopentadienyltris(sec-butylamino)Zirconium(IV) (Zr(TMG-Cp)(NHsBu)₃);(trimethylgermyl)cyclopentadienyl tris(Di tert-butylamino)Zirconium(IV)(Zr(TMG-Cp)(NtBu₂)₃); (trimethylgermyl)cyclopentadienyltris(tert-butylamino)Zirconium(IV) (Zr(TMG-Cp)(NHtBu)₃);(dimethylgermyl)cyclopentadienyl tris(Dimethylamino)Zirconium(IV)(Zr(DMG-Cp)(NMe₂)₃); (dimethylgermyl)cyclopentadienyltris(methylamino)Zirconium(IV) (Zr(DMG-Cp)(NHMe)₃);(dimethylgermyl)cyclopentadienyl tris(Diethylamino)Zirconium(IV)(Zr(DMG-Cp)(NEt₂)₃); (dimethylgermyl)cyclopentadienyltris(ethylamino)Zirconium(IV) (Zr(DMG-Cp)(NHEt)₃);(dimethylgermyl)cyclopentadienyl tris(ethylmethylamino) Zirconium(IV)(Zr(DMG-Cp)(NEtMe)₃); (dimethylgermyl)cyclopentadienyl tris(Din-propylamino)Zirconium(IV) (Zr(DMG-Cp)(NnPr₂)₃);(dimethylgermyl)cyclopentadienyl tris(n-propylamino)Zirconium(IV)(Zr(DMG-Cp)(NHnPr)₃); (dimethylgermyl)cyclopentadienyl tris(Diisopropylamino)Zirconium(IV) (Zr(DMG-Cp)(NiPr₂)₃);(dimethylgermyl)cyclopentadienyl tris(isopropylamino)Zirconium(IV)(Zr(DMG-Cp)(NHiPr)₃); (dimethylgermyl)cyclopentadienyl tris(Din-butylamino)Zirconium(IV) (Zr(DMG-Cp)(NnBu₂)₃);(dimethylgermyl)cyclopentadienyl tris(n-butylamino)Zirconium(IV)(Zr(DMG-Cp)(NHnBu)₃); (dimethylgermyl)cyclopentadienyl tris(Diisobutylamino)Zirconium(IV) (Zr(DMG-Cp)(NiBu₂)₃);(dimethylgermyl)cyclopentadienyl tris(isobutylamino)Zirconium(IV)(Zr(DMG-Cp)(NHiBu)₃); (dimethylgermyl)cyclopentadienyl tris(Disec-butylamino)Zirconium(IV) (Zr(DMG-Cp)(NsBu₂)₃);(dimethylgermyl)cyclopentadienyl tris(sec-butylamino)Zirconium(IV)(Zr(DMG-Cp)(NHsBu)₃); (dimethylgermyl)cyclopentadienyl tris(Ditert-butylamino)Zirconium(IV) (Zr(DMG-Cp)(NtBu₂)₃);(dimethylgermyl)cyclopentadienyl tris(tert-butylamino)Zirconium(IV)(Zr(DMG-Cp)(NHtBu)₃); (trifluorogermyl)cyclopentadienyltris(Dimethylamino)Zirconium(IV) (Zr(F₃Ge-Cp)(NMe₂)₃);(trifluorogermyl)cyclopentadienyl tris(methylamino)Zirconium(IV)(Zr(F₃Ge-Cp)(NHMe)₃); (trifluorogermyl)cyclopentadienyltris(Diethylamino) Zirconium(IV) (Zr(F₃Ge-Cp)(NEt₂)₃);(trifluorogermyl)cyclopentadienyl tris(ethylamino)Zirconium(IV)(Zr(F₃Ge-Cp)(NHEt)₃); (trifluorogermyl)cyclopentadienyltris(Ethylmethylamino)Zirconium(IV) (Zr(F₃Ge-Cp)(NEtMe)₃);(trifluorogermyl)cyclopentadienyl tris(Di n-propylamino)Zirconium(IV)(Zr(F₃Ge-Cp)(NnPr₂)₃); (trifluorogermyl)cyclopentadienyltris(n-propylamino)Zirconium(IV) (Zr(F₃Ge-Cp)(NHnPr)₃)(trifluorogermyl)cyclopentadienyl tris(Di isopropylamino)Zirconium(IV)(Zr(F₃Ge-Cp)(NiPr₂)₃); (trifluorogermyl)cyclopentadienyltris(isopropylamino)Zirconium(IV) (Zr(F₃Ge-Cp)(NHiPr)₃);(trifluorogermyl)cyclopentadienyl tris(Di n-butylamino)Zirconium(IV)(Zr(F₃Ge-Cp)(NnBu₂)₃); (trifluorogermyl)cyclopentadienyltris(n-butylamino)Zirconium(IV) (Zr(F₃Ge-Cp)(NHnBu)₃);(trifluorogermyl)cyclopentadienyl tris(Di isobutylamino)Zirconium(IV)(Zr(F₃Ge-Cp)(NiBu₂)₃); (trifluorogermyl)cyclopentadienyltris(isobutylamino)Zirconium(IV) (Zr(F₃Ge-Cp)(NHiBu)₃);(trifluorogermyl)cyclopentadienyl tris(Di sec-butylamino)Zirconium(IV)(Zr(F₃Ge-Cp)(NsBu₂)₃); (trifluorogermyl)cyclopentadienyltris(sec-butylamino)Zirconium(IV) (Zr(F₃Ge-Cp)(NHsBu)₃);(trifluorogermyl)cyclopentadienyl tris(Di tert-butylamino)Zirconium(IV)(Zr(F₃Ge-Cp)(NtBu₂)₃); (trifluorogermyl)cyclopentadienyltris(tert-butylamino)Zirconium(IV) (Zr(F₃Ge-Cp)(NHtBu)₃);(difluorogermyl)cyclopentadienyl tris(Dimethylamino)Zirconium(IV)(Zr(F₂HGe-Cp)(NMe₂)₃); (difluorogermyl)cyclopentadienyltris(methylamino)Zirconium(IV) (Zr(F₂HGe-Cp)(NHMe)₃);(difluorogermyl)cyclopentadienyl tris(Diethylamino)Zirconium(IV)(Zr(F₂HGe-Cp)(NEt₂)₃); (difluorogermyl)cyclopentadienyltris(ethylamino)Zirconium(IV) (Zr(F₂HGe-Cp)(NHEt)₃);(difluorogermyl)cyclopentadienyl tris(Ethylmethylamino) Zirconium(IV)(Zr(F₂HGe-Cp)(NEtMe)₃); (difluorogermyl)cyclopentadienyl tris(Din-propylamino)Zirconium(IV) (Zr(F₂HGe-Cp)(NnPr₂)₃);(difluorogermyl)cyclopentadienyl tris(n-propylamino)Zirconium(IV)(Zr(F₂HGe-Cp)(NHnPr)₃); (difluorogermyl)cyclopentadienyl tris(Diisopropylamino)Zirconium(IV) (Zr(F₂HGe-Cp)(NiPr₂)₃);(difluorogermyl)cyclopentadienyl tris(isopropylamino)Zirconium(IV)(Zr(F₂HGe-Cp)(NHiPr)₃); (difluorogermyl)cyclopentadienyl tris(Din-butylamino)Zirconium(IV) (Zr(F₂HGe-Cp)(NnBu₂)₃);(difluorogermyl)cyclopentadienyl tris(n-butylamino)Zirconium(IV)(Zr(F₂HGe-Cp)(NHnBu)₃); (difluorogermyl)cyclopentadienyl tris(Diisobutylamino)Zirconium(IV) (Zr(F₂HGe-Cp)(NiBu₂)₃);(difluorogermyl)cyclopentadienyl tris(isobutylamino)Zirconium(IV)(Zr(F₂HGe-Cp)(NHiBu)₃); (difluorogermyl)cyclopentadienyl tris(Disec-butylamino)Zirconium(IV) (Zr(F₂HGe-Cp)(NsBu₂)₃);(difluorogermyl)cyclopentadienyl tris(sec-butylamino)Zirconium(IV)(Zr(F₂HGe-Cp)(NHsBu)₃); (difluorogermyl)cyclopentadienyl tris(Ditert-butylamino)Zirconium(IV) (Zr(F₂HGe-Cp)(NtBu₂)₃);(difluorogermyl)cyclopentadienyl tris(tert-butylamino)Zirconium(IV)(Zr(F₂HGe-Cp)(NHtBu)₃); (monofluorogermyl)cyclopentadienyltris(Dimethylamino)Zirconium(IV) (Zr(FH₂Ge-Cp)(NMe₂)₃);(monofluorogermyl)cyclopentadienyl tris(methylamino)Zirconium(IV)(Zr(FH₂Ge-Cp)(NHMe)₃); (monofluorogermyl)cyclopentadienyltris(Diethylamino)Zirconium(IV) (Zr(FH₂Ge-Cp)(NEt₂)₃);(monofluorogermyl)cyclopentadienyl tris(ethylamino)Zirconium(IV)(Zr(FH₂Ge-Cp)(NHEO₃); (monofluorogermyl)cyclopentadienyltris(Ethylmethylamino)Zirconium(IV) (Zr(FH₂Ge-Cp)(NEtMe)₃);(monofluorogermyl)cyclopentadienyl tris(Di n-propylamino)Zirconium(IV)(Zr(FH₂Ge-Cp)(NnPr₂)₃); (monofluorogermyl)cyclopentadienyltris(n-propylamino)Zirconium(IV) (Zr(FH₂Ge-Cp)(NHnPr)₃);(monofluorogermyl)cyclopentadienyl tris(Diisopropylamino)Zirconium(IV)(Zr(FH₂Ge-Cp)(NiPr₂)₃); (monofluorogermyl)cyclopentadienyltris(isopropylamino)Zirconium(IV) (Zr(FH₂Ge-Cp)(NHiPr)₃);(monofluorogermyl)cyclopentadienyl tris(Di n-butylamino)Zirconium(IV)(Zr(FH₂Ge-Cp)(NnBu₂)₃); (monofluorogermyl)cyclopentadienyltris(n-butylamino)Zirconium(IV) (Zr(FH₂Ge-Cp)(NHnBu)₃);(monofluorogermyl)cyclopentadienyl tris(Di isobutylamino)Zirconium(IV)(Zr(FH₂Ge-Cp)(NiBu₂)₃) (monofluorogermyl)cyclopentadienyltris(isobutylamino)Zirconium(IV) (Zr(FH₂Ge-Cp)(NHiBu)₃);(monofluorogermyl)cyclopentadienyl tris(Di sec-butylamino)Zirconium(IV)(Zr(FH₂Ge-Cp)(NsBu₂)₃); (monofluorogermyl)cyclopentadienyltris(sec-butylamino)Zirconium(IV) (Zr(FH₂Ge-Cp)(NHsBO₃);(monofluorogermyl)cyclopentadienyl tris(Di tert-butylamino)Zirconium(IV)(Zr(FH₂Ge-Cp)(NtBu₂)₃); (monofluorogermyl)cyclopentadienyltris(tert-butylamino)Zirconium(IV) (Zr(FH₂Ge-Cp)(NHtBu)₃); (fluorodimethylgermyl)cyclopentadienyl tris(Dimethylamino) Zirconium(IV)(Zr(FMe₂Ge-Cp)(NMe₂)₃); (fluoro dimethylgermyl)cyclopentadienyltris(methylamino)Zirconium(IV) (Zr(FMe₂Ge-Cp)(NHMe)₃); (fluorodimethylgermyl)cyclopentadienyl tris(Diethylamino)Zirconium(IV)(Zr(FMe₂Ge-Cp)(NEt₂)₃); (fluoro dimethylgermyl)cyclopentadienyltris(ethylamino)Zirconium(IV) (Zr(FMe₂Ge-Cp)(NHEt)₃); (fluorodimethylgermyl)cyclopentadienyl tris(Ethylmethylamino)Zirconium(IV)(Zr(FMe₂Ge-Cp)(NEtMe)₃); (fluoro dimethylgermyl)cyclopentadienyl tris(Din-propylamino) Zirconium(IV) (Zr(FMe₂Ge-Cp)(NnPr₂)₃); (fluorodimethylgermyl)cyclopentadienyl tris(n-propylamino)Zirconium(IV)(Zr(FMe₂Ge-Cp)(NHnPr)₃); (fluoro dimethylgermyl)cyclopentadienyltris(Diisopropylamino)Zirconium(IV) (Zr(FMe₂Ge-Cp)(NiPr₂)₃); (fluorodimethylgermyl)cyclopentadienyl tris(isopropylamino) Zirconium(IV)(Zr(FMe₂Ge-Cp)(NHiPr)₃); (fluoro dimethylgermyl)cyclopentadienyl tris(Din-butylamino)Zirconium(IV) (Zr(FMe₂Ge-Cp)(NnBu₂)₃); (fluorodimethylgermyl)cyclopentadienyl tris(n-butylamino)Zirconium(IV)(Zr(FMe₂Ge-Cp)(NHnBu)₃); (fluoro dimethylgermyl)cyclopentadienyl tris(Diisobutylamino)Zirconium(IV) (Zr(FMe₂Ge-Cp)(NiBu₂)₃); (fluorodimethylgermyl)cyclopentadienyl tris(isobutylamino) Zirconium(IV)(Zr(FMe₂Ge-Cp)(NHiBu)₃); (fluoro dimethylgermyl)cyclopentadienyl tris(Disec-butylamino) Zirconium(IV) (Zr(FMe₂Ge-Cp)(NsBu₂)₃); (fluorodimethylgermyl)cyclopentadienyl tris(sec-butylamino)Zirconium(IV)(Zr(FMe₂Ge-Cp)(NHsBu)₃); (fluoro dimethylgermyl)cyclopentadienyl tris(Ditert-butylamino)Zirconium(IV) (Zr(FMe₂Ge-Cp)(NtBu₂)₃); (fluorodimethylgermyl)cyclopentadienyl tris(tert-butylamino) Zirconium(IV)(Zr(FMe₂Ge-Cp)(NHtBu)₃); (tris(trifluoromethyl)germyl)cyclopentadienyltris(Dimethylamino) Zirconium(IV) (Zr((CF₃)₃Ge-Cp)(NMe₂)₃);(tris(trifluoromethyl)germyl)cyclopentadienyl tris(methylamino)Zirconium(IV) (Zr((CF₃)₃Ge-Cp)(NHMe)₃);(tris(trifluoromethyl)germyl)cyclopentadienyl tris(Diethylamino)Zirconium(IV) (Zr((CF₃)₃Ge-Cp)(NEt₂)₃);(tris(trifluoromethyl)germyl)cyclopentadienyl tris(ethylamino)Zirconium(IV) (Zr((CF₃)₃Ge-Cp)(NHEt)₃);(tris(trifluoromethyl)germyl)cyclopentadienyl tris(Ethylmethylamino)Zirconium(IV) (Zr((CF₃)₃Ge-Cp)(NEtMe)₃);(tris(trifluoromethyl)germyl)cyclopentadienyl tris(Di n-propylamino)Zirconium(IV) (Zr((CF₃)₃Ge-Cp)(NnPr₂)₃);(tris(trifluoromethyl)germyl)cyclopentadienyl tris(n-propylamino)Zirconium(IV) (Zr((CF₃)₃Ge-Cp)(NHnPr)₃);(tris(trifluoromethyl)germyl)cyclopentadienyl tris(Diisopropylamino)Zirconium(IV) (Zr((CF₃)₃Ge-Cp)(NiPr₂)₃);(tris(trifluoromethyl)germyl)cyclopentadienyl tris(isopropylamino)Zirconium(IV) (Zr((CF₃)₃Ge-Cp)(NHiPr)₃);(tris(trifluoromethyl)germyl)cyclopentadienyl tris(Di n-butylamino)Zirconium(IV) (Zr((CF₃)₃Ge-Cp)(NnBu₂)₃);(tris(trifluoromethyl)germyl)cyclopentadienyl tris(n-butylamino)Zirconium(IV) (Zr((CF₃)₃Ge-Cp)(NHnBu)₃);(tris(trifluoromethyl)germyl)cyclopentadienyl tris(Di isobutylamino)Zirconium(IV) (Zr((CF₃)₃Ge-Cp)(NiBu₂)₃);(tris(trifluoromethyl)germyl)cyclopentadienyl tris(isobutylamino)Zirconium(IV) (Zr((CF₃)₃Ge-Cp)(NHiBu)₃);(tris(trifluoromethyl)germyl)cyclopentadienyl tris(Di sec-butylamino)Zirconium(IV) (Zr((CF₃)₃Ge-Cp)(NsBu₂)₃);(tris(trifluoromethyl)germyl)cyclopentadienyl tris(sec-butylamino)Zirconium(IV) (Zr((CF₃)₃Ge-Cp)(NHsBu)₃);(tris(trifluoromethyl)germyl)cyclopentadienyl tris(Di tert-butylamino)Zirconium(IV) (Zr((CF₃)₃Ge-Cp)(NtBu₂)₃);(tris(trifluoromethyl)germyl)cyclopentadienyl tris(tert-butylamino)Zirconium(IV) (Zr((CF₃)₃Ge-Cp)(NHtBu)₃);(bis(trifluoromethyl)germyl)cyclopentadienyl tris(Dimethylamino)Zirconium(IV) (Zr((CF₃)₂HGe-Cp)(NMe₂)₃);(bis(trifluoromethyl)germyl)cyclopentadienyl tris(methylamino)Zirconium(IV) (Zr((CF₃)₂HGe-Cp)(NHMe)₃);(bis(trifluoromethyl)germyl)cyclopentadienyl tris(Diethylamino)Zirconium(IV) (Zr((CF₃)₂HGe-Cp)(NEt₂)₃);(bis(trifluoromethyl)germyl)cyclopentadienyl tris(ethylamino)Zirconium(IV) (Zr((CF₃)₂HGe-Cp)(NHEt)₃);(bis(trifluoromethyl)germyl)cyclopentadienyl tris(Ethylmethylamino)Zirconium(IV) (Zr((CF₃)₂HGe-Cp)(NEtMe)₃);(bis(trifluoromethyl)germyl)cyclopentadienyl tris(Di n-propylamino)Zirconium(IV) (Zr((CF₃)₂HGe-Cp)(NnPr₂)₃);(bis(trifluoromethyl)germyl)cyclopentadienyl tris(n-propylamino)Zirconium(IV) (Zr((CF₃)₂HGe-Cp)(NHnPr)₃);(bis(trifluoromethyl)germyl)cyclopentadienyl tris(Diisopropylamino)Zirconium(IV) (Zr((CF₃)₂HGe-Cp)(NiPr₂)₃);(bis(trifluoromethyl)germyl)cyclopentadienyl tris(isopropylamino)Zirconium(IV) (Zr((CF₃)₂HGe-Cp)(NHiPr)₃);(bis(trifluoromethyl)germyl)cyclopentadienyl tris(Di n-butylamino)Zirconium(IV) (Zr((CF₃)₂HGe-Cp)(NnBu₂)₃);(bis(trifluoromethyl)germyl)cyclopentadienyl tris(n-butylamino)Zirconium(IV) (Zr((CF₃)₂HGe-Cp)(NHnBu)₃);(bis(trifluoromethyl)germyl)cyclopentadienyl tris(Di isobutylamino)Zirconium(IV) (Zr((CF₃)₂HGe-Cp)(NiBu₂)₃);(bis(trifluoromethyl)germyl)cyclopentadienyl tris(isobutylamino)Zirconium(IV) (Zr((CF₃)₂HGe-Cp)(NHiBu)₃);(bis(trifluoromethyl)germyl)cyclopentadienyl tris(Di sec-butylamino)Zirconium(IV) (Zr((CF₃)₂HGe-Cp)(NsBu₂)₃);(bis(trifluoromethyl)germyl)cyclopentadienyl tris(sec-butylamino)Zirconium(IV) (Zr((CF₃)₂HGe-Cp)(NHsBu)₃);(bis(trifluoromethyl)germyl)cyclopentadienyl tris(Di tert-butylamino)Zirconium(IV) (Zr((CF₃)₂HGe-Cp)(NtBu₂)₃);(bis(trifluoromethyl)germyl)cyclopentadienyl tris(tert-butylamino)Zirconium(IV) (Zr((CF₃)₂HGe-Cp)(NHtBu)₃);((trifluoromethyl)dimethylgermyl)cyclopentadienyl tris(Dimethylamino)Zirconium(IV) (Zr((CF₃)Me₂Ge-Cp)(NMe₂)₃);((trifluoromethyl)dimethylgermyl)cyclopentadienyl tris(methylamino)Zirconium(IV) (Zr((CF₃)Me₂Ge-Cp)(NHMe)₃);((trifluoromethyl)dimethylgermyl)cyclopentadienyl tris(Diethylamino)Zirconium(IV) (Zr((CF₃)Me₂Ge-Cp)(NEt₂)₃);((trifluoromethyl)dimethylgermyl)cyclopentadienyl tris(ethylamino)Zirconium(IV) (Zr((CF₃)Me₂Ge-Cp)(NHEt)₃);((trifluoromethyl)dimethylgermyl)cyclopentadienyltris(Ethylmethylamino)Zirconium(IV) (Zr((CF₃)Me₂Ge-Cp)(NEtMe)₃);((trifluoromethyl)dimethylgermyl)cyclopentadienyl tris(Din-propylamino)Zirconium(IV) (Zr((CF₃)Me₂Ge-Cp)(NnPr₂)₃);((trifluoromethyl)dimethylgermyl)cyclopentadienyl tris(n-propylamino)Zirconium(IV) (Zr((CF₃)Me₂Ge-Cp)(NHnPr)₃);((trifluoromethyl)dimethylgermyl)cyclopentadienyl tris(Diisopropylamino)Zirconium(IV) (Zr((CF₃)Me₂Ge-Cp)(NiPr₂)₃);((trifluoromethyl)dimethylgermyl)cyclopentadienyl tris(isopropylamino)Zirconium(IV) (Zr((CF₃)Me₂Ge-Cp)(NHiPr)₃);((trifluoromethyl)dimethylgermyl)cyclopentadienyl tris(Din-butylamino)Zirconium(IV) (Zr((CF₃)Me₂Ge-Cp)(NnBu₂)₃);((trifluoromethyl)dimethylgermyl)cyclopentadienyl tris(n-butylamino)Zirconium(IV) (Zr((CF₃)Me₂Ge-Cp)(NHnBu)₃);((trifluoromethyl)dimethylgermyl)cyclopentadienyl tris(Diisobutylamino)Zirconium(IV) (Zr((CF₃)Me₂Ge-Cp)(NiBu₂)₃);((trifluoromethyl)dimethylgermyl)cyclopentadienyl tris(isobutylamino)Zirconium(IV) (Zr((CF₃)Me₂Ge-Cp)(NHiBu)₃);((trifluoromethyl)dimethylgermyl)cyclopentadienyl tris(Disec-butylamino)Zirconium(IV) (Zr((CF₃)Me₂Ge-Cp)(NsBu₂)₃);((trifluoromethyl)dimethylgermyl)cyclopentadienyl tris(sec-butylamino)Zirconium(IV) (Zr((CF₃)Me₂Ge-Cp)(NHsBu)₃);((trifluoromethyl)dimethylgermyl)cyclopentadienyl tris(Ditert-butylamino)Zirconium(IV) (Zr((CF₃)Me₂Ge-Cp)(NtBu₂)₃); and((trifluoromethyl)dimethylgermyl)cyclopentadienyl tris(tert-butylamino)Zirconium(IV) (Zr((CF₃)Me₂Ge-Cp)(NHtBu)₃).
 4. The Germanium- andZirconium-film forming composition of claim 3, wherein the precursor is(trimethylgermyl)cyclopentadienyl tris(dimethylamino)Zirconium(IV)[Zr(TMG-Cp)(NMe₂)₃].
 5. The Germanium- and Zirconium-film formingcomposition of claim 1, having the Formula II:


6. The Germanium- and Zirconium-film forming composition of claim 5,wherein the precursor is selected from the group consisting of:(trimethylgermyl)cyclopentadienyl tris(methoxy)Zirconium(IV)(Zr(TMG-Cp)(OMe)₃); (trimethylgermyl)cyclopentadienyltris(ethoxy)Zirconium(IV) (Zr(TMG-Cp)(OEt)₃);(trimethylgermyl)cyclopentadienyl tris(n-propoxy) Zirconium(IV)(Zr(TMG-Cp)(OnPr)₃); (trimethylgermyl)cyclopentadienyltris(isopropoxy)Zirconium(IV) (Zr(TMG-Cp)(OiPr)₃);(trimethylgermyl)cyclopentadienyl tris(tert-butoxy)Zirconium(IV)(Zr(TMG-Cp)(OtBu)₃); (trimethylgermyl)cyclopentadienyl tris(sec-butoxy)Zirconium(IV) (Zr(TMG-Cp)(OsBu)₃); (trimethylgermyl)cyclopentadienyltris(n-butoxy)Zirconium(IV) (Zr(TMG-Cp)(OnBu)₃);(trimethylgermyl)cyclopentadienyl tris(iso-butoxy)Zirconium(IV)(Zr(TMG-Cp)(OiBu)₃); (dimethylgermyl)cyclopentadienyltris(methoxy)Zirconium(IV) (Zr(DMG-Cp)(OMe)₃);(dimethylgermyl)cyclopentadienyl tris(ethoxy) Zirconium(IV)(Zr(DMG-Cp)(OEt)₃); (dimethylgermyl)cyclopentadienyltris(n-propoxy)Zirconium(IV) (Zr(DMG-Cp)(OnPr)₃);(dimethylgermyl)cyclopentadienyl tris(isopropoxy)Zirconium(IV)(Zr(DMG-Cp)(OiPr)₃); (dimethylgermyl)cyclopentadienyl tris(tert-butoxy)Zirconium(IV) (Zr(DM G-Cp)(OtBu)₃); (dimethylgermyl)cyclopentadienyltris(sec-butoxy)Zirconium(IV) (Zr(DMG-Cp)(OsBu)₃);(dimethylgermyl)cyclopentadienyl tris(n-butoxy)Zirconium(IV)(Zr(DMG-Cp)(OnBu)₃); (dimethylgermyl)cyclopentadienyl tris(isobutoxy)Zirconium(IV) (Zr(DM G-Cp)(0i Bu)₃); (trifluorogermyl)cyclopentadienyltris(methoxy)Zirconium(IV) (Zr(F₃Ge-Cp)(OMe)₃);(trifluorogermyl)cyclopentadienyl tris(ethoxy)Zirconium(IV)(Zr(F₃Ge-Cp)(OEt)₃); (trifluorogermyl)cyclopentadienyltris(n-propoxy)Zirconium(IV) (Zr(F₃Ge-Cp)(OnPr)₃);(trifluorogermyl)cyclopentadienyl tris(isopropoxy) Zirconium(IV)(Zr(F₃Ge-Cp)(OiPr)₃); (trifluorogermyl)cyclopentadienyltris(tert-butoxy)Zirconium(IV) (Zr(F₃Ge-Cp)(OtBu)₃);(trifluorogermyl)cyclopentadienyl tris(sec-butoxy)Zirconium(IV)(Zr(F₃Ge-Cp)(OsBu)₃); (trifluorogermyl)cyclopentadienyltris(n-butoxy)Zirconium(IV) (Zr(F₃Ge-Cp)(OnBu)₃);(trifluorogermyl)cyclopentadienyl tris(isobutoxy) Zirconium(IV)(Zr(F₃Ge-Cp)(OiBu)₃); (difluorogermyl)cyclopentadienyltris(methoxy)Zirconium(IV) (Zr(F₂HGe-Cp)(OMe)₃);(difluorogermyl)cyclopentadienyl tris(ethoxy)Zirconium(IV)(Zr(F₂HGe-Cp)(OEt)₃); (difluorogermyl)cyclopentadienyltris(n-propoxy)Zirconium(IV) (Zr(F₂HGe-Cp)(OnPr)₃);(difluorogermyl)cyclopentadienyl tris(isopropoxy) Zirconium(IV)(Zr(F₂HGe-Cp)(OiPr)₃); (difluorogermyl)cyclopentadienyltris(tert-butoxy)Zirconium(IV) (Zr(F₂HGe-Cp)(OtBu)₃);(difluorogermyl)cyclopentadienyl tris(sec-butoxy)Zirconium(IV)(Zr(F₂HGe-Cp)(OsBu)₃); (difluorogermyl)cyclopentadienyltris(n-butoxy)Zirconium(IV) (Zr(F₂HGe-Cp)(OnBu)₃);(difluorogermyl)cyclopentadienyl tris(isobutoxy)Zirconium(IV)(Zr(F₂HGe-Cp)(OiBu)₃); (monofluorogermyl)cyclopentadienyltris(methoxy)Zirconium(IV) (Zr(FH₂Ge-Cp)(OMe)₃);(monofluorogermyl)cyclopentadienyl tris(ethoxy)Zirconium(IV)(Zr(FH₂Ge-Cp)(OEt)₃); (monofluorogermyl)cyclopentadienyltris(n-propoxy)Zirconium(IV) (Zr(FH₂Ge-Cp)(OnPr)₃);(monofluorogermyl)cyclopentadienyl tris(isopropoxy)Zirconium(IV)(Zr(FH₂Ge-Cp)(OiPr)₃); (monofluorogermyl)cyclopentadienyltris(tert-butoxy)Zirconium(IV) (Zr(FH₂Ge-Cp)(OtBu)₃);(monofluorogermyl)cyclopentadienyl tris(sec-butoxy)Zirconium(IV)(Zr(FH₂Ge-Cp)(OsBu)₃); (monofluorogermyl)cyclopentadienyltris(n-butoxy)Zirconium(IV) (Zr(FH₂Ge-Cp)(OnBu)₃);(monofluorogermyl)cyclopentadienyl tris(isobutoxy)Zirconium(IV)(Zr(FH₂Ge-Cp)(OiBu)₃); (fluoro dimethylgermyl)cyclopentadienyltris(methoxy)Zirconium(IV) (Zr(FMe₂Ge-Cp)(OMe)₃); (fluorodimethylgermyl)cyclopentadienyl tris(ethoxy)Zirconium(IV)(Zr(FMe₂Ge-Cp)(OEt)₃); (fluoro dimethylgermyl)cyclopentadienyltris(n-propoxy)Zirconium(IV) (Zr(FMe₂Ge-Cp)(OnPr)₃); (fluorodimethylgermyl)cyclopentadienyl tris(isopropoxy)Zirconium(IV)(Zr(FMe₂Ge-Cp)(OiPr)₃); (fluoro dimethylgermyl)cyclopentadienyltris(tert-butoxy)Zirconium(IV) (Zr(FMe₂Ge-Cp)(OtBu)₃); (fluorodimethylgermyl)cyclopentadienyl tris(sec-butoxy)Zirconium(IV)(Zr(FMe₂Ge-Cp)(OsBu)₃); (fluoro dimethylgermyl)cyclopentadienyltris(n-butoxy)Zirconium(IV) (Zr(FMe₂Ge-Cp)(OnBu)₃); (fluorodimethylgermyl)cyclopentadienyl tris(isobutoxy)Zirconium(IV)(Zr(FMe₂Ge-Cp)(OiBu)₃); (tris(trifluoromethyl)germyl)cyclopentadienyltris(methoxy) Zirconium(IV) (Zr((CF₃)₃Ge-Cp)(OMe)₃);(tris(trifluoromethyl)germyl)cyclopentadienyl tris(ethoxy)Zirconium(IV)(Zr((CF₃)₃Ge-Cp)(OEt)₃); (tris(trifluoromethyl)germyl)cyclopentadienyltris(n-propoxy) Zirconium(IV) (Zr((CF₃)₃Ge-Cp)(OnPr)₃);(tris(trifluoromethyl)germyl)cyclopentadienyl tris(isopropoxy)Zirconium(IV) (Zr((CF₃)₃Ge-Cp)(OiPr)₃);(tris(trifluoromethyl)germyl)cyclopentadienyl tris(tert-butoxy)Zirconium(IV) (Zr((CF₃)₃Ge-Cp)(OtBu)₃);(tris(trifluoromethyl)germyl)cyclopentadienyl tris(sec-butoxy)Zirconium(IV) (Zr((CF₃)₃Ge-Cp)(OsBu)₃);(tris(trifluoromethyl)germyl)cyclopentadienyl tris(n-butoxy)Zirconium(IV) (Zr((CF₃)₃Ge-Cp)(OnBu)₃);(tris(trifluoromethyl)germyl)cyclopentadienyl tris(isobutoxy)Zirconium(IV) (Zr((CF₃)₃Ge-Cp)(OiBu)₃);(bis(trifluoromethyl)germyl)cyclopentadienyl tris(methoxy) Zirconium(IV)(Zr((CF₃)₂HGe-Cp)(OMe)₃); (bis(trifluoromethyl)germyl)cyclopentadienyltris(ethoxy)Zirconium(IV) (Zr((CF₃)₂HGe-CP)(OEt)₃);(bis(trifluoromethyl)germyl)cyclopentadienyl tris(n-propoxy)Zirconium(IV) (Zr((CF₃)₂HGe-Cp)(OnPr)₃);(bis(trifluoromethyl)germyl)cyclopentadienyl tris(isopropoxy)Zirconium(IV) (Zr((CF₃)₂HGe-Cp)(OiPr)₃);(bis(trifluoromethyl)germyl)cyclopentadienyl tris(tert-butoxy)Zirconium(IV) (Zr((CF₃)₂HGe-Cp)(OtBu)₃);(bis(trifluoromethyl)germyl)cyclopentadienyl tris(sec-butoxy)Zirconium(IV) (Zr((CF₃)₂HGe-Cp)(OsBu)₃);(bis(trifluoromethyl)germyl)cyclopentadienyl tris(n-butoxy)Zirconium(IV) (Zr((CF₃)₂HGe-Cp)(OnBu)₃);(bis(trifluoromethyl)germyl)cyclopentadienyl tris(iso-butoxy)Zirconium(IV) (Zr((CF₃)₂HGe-Cp)(OiBu)₃);((trifluoromethyl)dimethylgermyl)cyclopentadienyl tris(methoxy)Zirconium(IV) (Zr((CF₃)Me₂Ge-Cp)(OMe)₃);((trifluoromethyl)dimethylgermyl)cyclopentadienyl tris(ethoxy)Zirconium(IV) (Zr((CF₃)Me₂Ge-Cp)(OEt)₃);((trifluoromethyl)dimethylgermyl)cyclopentadienyl tris(n-propoxy)Zirconium(IV) (Zr((CF₃)Me₂Ge-Cp)(OnPr)₃);((trifluoromethyl)dimethylgermyl)cyclopentadienyl tris(isopropoxy)Zirconium(IV) (Zr((CF₃)Me₂Ge-Cp)(OiPr)₃);((trifluoromethyl)dimethylgermyl)cyclopentadienyl tris(tert-butoxy)Zirconium(IV) (Zr((CF₃)Me₂Ge-Cp)(OtBu)₃);((trifluoromethyl)dimethylgermyl)cyclopentadienyl tris(sec-butoxy)Zirconium(IV) (Zr((CF₃)Me₂Ge-Cp)(OsBu)₃);((trifluoromethyl)dimethylgermyl)cyclopentadienyl tris(n-butoxy)Zirconium(IV) (Zr((CF₃)Me₂Ge-Cp)(OnBu)₃); and((trifluoromethyl)dimethylgermyl)cyclopentadienyl tris(isobutoxy)Zirconium(IV) (Zr((CF₃)Me₂Ge-Cp)(OiBu)₃).
 7. The Germanium- andZirconium-film forming composition of claim 6, wherein the precursor is(trimethylgermyl)cyclopentadienyl tris(isopropoxy) Zirconium(IV)[Zr(TMG-Cp)(OiPr)₃].
 8. The Germanium- and Zirconium-film formingcomposition of claim 1, the composition comprising between approximately95% w/w and approximately 100% w/w of the precursor.
 9. The Germanium-and Zirconium-film forming composition of claim 1, the compositioncomprising between approximately 0.0% w/w and approximately 5.0% w/wimpurities.
 10. The Germanium- and Zirconium-film forming composition ofclaim 9, the impurities including alcohol; alkylamines; dialkylamines;alkylimines; cyclopentadiene; dicyclopentadiene; alkylgermane; THF;ether; pentane; cyclohexane; heptane; benzene; toluene; chlorinatedmetal compounds; lithium, sodium, or potassium alkylamino; lithium,sodium, or potassium alkylakoxy; and/or lithium, sodium, or potassiumcyclopentadienyl.
 11. The Germanium- and Zirconium-film formingcomposition of claim 1, the composition comprising between approximately0 ppbw and approximately 1 ppmw metal impurities.
 12. The Germanium- andZirconium-film forming composition of claim 11, the metal impuritiesincluding Aluminum (Al), Arsenic (As), Barium (Ba), Beryllium (Be),Bismuth (Bi), Cadmium (Cd), Calcium (Ca), Chromium (Cr), Cobalt (Co),Copper (Cu), Gallium (Ga), Germanium (Ge), Hafnium (Hf), Zirconium (Zr),Indium (In), Iron (Fe), Lead (Pb), Lithium (Li), Magnesium (Mg),Manganese (Mn), Tungsten (W), Nickel (Ni), Potassium (K), Sodium (Na),Strontium (Sr), Thorium (Th), Tin (Sn), Titanium (Ti), Uranium (U),and/or Zinc (Zn).
 13. A process for the deposition of aZirconium-containing film on a substrate, the process comprising thesteps of: introducing a vapor of the Germanium- and Zirconium-containingprecursor into a reactor having a substrate disposed therein anddepositing at least part of the Germanium- and Zirconium-containingprecursor onto the substrate, the precursor having one of the followingformulae:

wherein each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹ and R¹⁰ is independentlyselected from the group consisting of H; a C1-C5 linear, branched, orcyclic alkyl group; and a C1-C5 linear, branched, or cyclic fluoroalkylgroup.
 14. The process of claim 13, wherein the Germanium- andZirconium-containing precursor is selected from the group consisting of:(trimethylgermyl)cyclopentadienyl tris(Dimethylamino)Zirconium(IV)(Zr(TMG-Cp)(NMe₂)₃); (trimethylgermyl)cyclopentadienyl tris(methylamino)Zirconium(IV) (Zr(TMG-Cp)(NHMe)₃); (trimethylgermyl)cyclopentadienyltris(Diethylamino)Zirconium(IV) (Zr(TMG-Cp)(NEt₂)₃);(trimethylgermyl)cyclopentadienyl tris(ethylamino)Zirconium(IV)(Zr(TMG-Cp)(NHEt)₃); (trimethylgermyl)cyclopentadienyltris(ethylmethylamino) Zirconium(IV) (Zr(TMG-Cp)(NEtMe)₃);(trimethylgermyl)cyclopentadienyl tris(Di n-propylamino)Zirconium(IV)(Zr(TMG-Cp)(NnPr₂)₃); (trimethylgermyl)cyclopentadienyltris(n-propylamino)Zirconium(IV) (Zr(TMG-Cp)(NHnPr)₃);(trimethylgermyl)cyclopentadienyl tris(Di isopropylamino)Zirconium(IV)(Zr(TMG-Cp)(NiPr₂)₃); (trimethylgermyl)cyclopentadienyltris(isopropylamino)Zirconium(IV) (Zr(TMG-Cp)(NH iPr)₃);(trimethylgermyl)cyclopentadienyl tris(Di n-butylamino)Zirconium(IV)(Zr(TMG-Cp)(NnBu₂)₃); (trimethylgermyl)cyclopentadienyltris(n-butylamino)Zirconium(IV) (Zr(TMG-Cp)(NHnBu)₃)(trimethylgermyl)cyclopentadienyl tris(Di isobutylamino)Zirconium(IV)(Zr(TMG-Cp)(NiBu₂)₃); (trimethylgermyl)cyclopentadienyltris(isobutylamino)Zirconium(IV) (Zr(TMG-Cp)(NHiBu)₃);(trimethylgermyl)cyclopentadienyl tris(Di sec-butylamino)Zirconium(IV)(Zr(TMG-Cp)(NsBu₂)₃); (trimethylgermyl)cyclopentadienyltris(sec-butylamino)Zirconium(IV) (Zr(TMG-Cp)(NHsBu)₃);(trimethylgermyl)cyclopentadienyl tris(Di tert-butylamino)Zirconium(IV)(Zr(TMG-Cp)(NtBu₂)₃); (trimethylgermyl)cyclopentadienyltris(tert-butylamino)Zirconium(IV) (Zr(TMG-Cp)(NHtBu)₃);(dimethylgermyl)cyclopentadienyl tris(Dimethylamino)Zirconium(IV)(Zr(DMG-Cp)(NMe₂)₃); (dimethylgermyl)cyclopentadienyltris(methylamino)Zirconium(IV) (Zr(DMG-Cp)(NHMe)₃);(dimethylgermyl)cyclopentadienyl tris(Diethylamino)Zirconium(IV)(Zr(DMG-Cp)(NEt₂)₃); (dimethylgermyl)cyclopentadienyltris(ethylamino)Zirconium(IV) (Zr(DMG-Cp)(NHEt)₃);(dimethylgermyl)cyclopentadienyl tris(ethylmethylamino) Zirconium(IV)(Zr(DMG-Cp)(NEtMe)₃); (dimethylgermyl)cyclopentadienyl tris(Din-propylamino)Zirconium(IV) (Zr(DMG-Cp)(NnPr₂)₃);(dimethylgermyl)cyclopentadienyl tris(n-propylamino)Zirconium(IV)(Zr(DMG-Cp)(NHnPr)₃); (dimethylgermyl)cyclopentadienyl tris(Diisopropylamino)Zirconium(IV) (Zr(DMG-Cp)(NiPr₂)₃);(dimethylgermyl)cyclopentadienyl tris(isopropylamino)Zirconium(IV)(Zr(DMG-Cp)(NH iPr)₃); (dimethylgermyl)cyclopentadienyl tris(Din-butylamino)Zirconium(IV) (Zr(DMG-Cp)(NnBu₂)₃);(dimethylgermyl)cyclopentadienyl tris(n-butylamino)Zirconium(IV)(Zr(DMG-Cp)(NHnBu)₃); (dimethylgermyl)cyclopentadienyl tris(Diisobutylamino)Zirconium(IV) (Zr(DMG-Cp)(NiBu₂)₃);(dimethylgermyl)cyclopentadienyl tris(isobutylamino)Zirconium(IV)(Zr(DMG-Cp)(NHiBu)₃); (dimethylgermyl)cyclopentadienyl tris(Disec-butylamino)Zirconium(IV) (Zr(DMG-Cp)(NsBu₂)₃);(dimethylgermyl)cyclopentadienyl tris(sec-butylamino)Zirconium(IV)(Zr(DMG-Cp)(NHsBu)₃); (dimethylgermyl)cyclopentadienyl tris(Ditert-butylamino)Zirconium(IV) (Zr(DMG-Cp)(NtBu₂)₃);(dimethylgermyl)cyclopentadienyl tris(tert-butylamino)Zirconium(IV)(Zr(DMG-Cp)(NHtBu)₃); (trifluorogermyl)cyclopentadienyltris(Dimethylamino)Zirconium(IV) (Zr(F₃Ge-Cp)(NMe₂)₃);(trifluorogermyl)cyclopentadienyl tris(methylamino)Zirconium(IV)(Zr(F₃Ge-Cp)(NHMe)₃); (trifluorogermyl)cyclopentadienyltris(Diethylamino) Zirconium(IV) (Zr(F₃Ge-Cp)(NEt₂)₃);(trifluorogermyl)cyclopentadienyl tris(ethylamino)Zirconium(IV)(Zr(F₃Ge-Cp)(NHEt)₃); (trifluorogermyl)cyclopentadienyltris(Ethylmethylamino)Zirconium(IV) (Zr(F₃Ge-Cp)(NEtMe)₃);(trifluorogermyl)cyclopentadienyl tris(Di n-propylamino)Zirconium(IV)(Zr(F₃Ge-Cp)(NnPr₂)₃); (trifluorogermyl)cyclopentadienyltris(n-propylamino)Zirconium(IV) (Zr(F₃Ge-Cp)(NHnPr)₃)(trifluorogermyl)cyclopentadienyl tris(Di isopropylamino)Zirconium(IV)(Zr(F₃Ge-Cp)(NiPr₂)₃); (trifluorogermyl)cyclopentadienyltris(isopropylamino)Zirconium(IV) (Zr(F₃Ge-Cp)(NHiPr)₃);(trifluorogermyl)cyclopentadienyl tris(Di n-butylamino)Zirconium(IV)(Zr(F₃Ge-Cp)(NnBu₂)₃); (trifluorogermyl)cyclopentadienyltris(n-butylamino)Zirconium(IV) (Zr(F₃Ge-Cp)(NHnBu)₃);(trifluorogermyl)cyclopentadienyl tris(Di isobutylamino)Zirconium(IV)(Zr(F₃Ge-Cp)(NiBu₂)₃); (trifluorogermyl)cyclopentadienyltris(isobutylamino)Zirconium(IV) (Zr(F₃Ge-Cp)(NHiBu)₃);(trifluorogermyl)cyclopentadienyl tris(Di sec-butylamino)Zirconium(IV)(Zr(F₃Ge-Cp)(NsBu₂)₃); (trifluorogermyl)cyclopentadienyltris(sec-butylamino)Zirconium(IV) (Zr(F₃Ge-Cp)(NHsBu)₃);(trifluorogermyl)cyclopentadienyl tris(Di tert-butylamino)Zirconium(IV)(Zr(F₃Ge-Cp)(NtBu₂)₃); (trifluorogermyl)cyclopentadienyltris(tert-butylamino)Zirconium(IV) (Zr(F₃Ge-Cp)(NHtBu)₃);(difluorogermyl)cyclopentadienyl tris(Dimethylamino)Zirconium(IV)(Zr(F₂HGe-Cp)(NMe₂)₃); (difluorogermyl)cyclopentadienyltris(methylamino)Zirconium(IV) (Zr(F₂HGe-Cp)(NHMe)₃);(difluorogermyl)cyclopentadienyl tris(Diethylamino)Zirconium(IV)(Zr(F₂HGe-Cp)(NEt₂)₃); (difluorogermyl)cyclopentadienyltris(ethylamino)Zirconium(IV) (Zr(F₂HGe-Cp)(NHEt)₃);(difluorogermyl)cyclopentadienyl tris(Ethylmethylamino) Zirconium(IV)(Zr(F₂HGe-Cp)(NEtMe)₃); (difluorogermyl)cyclopentadienyl tris(Din-propylamino)Zirconium(IV) (Zr(F₂HGe-Cp)(NnPr₂)₃);(difluorogermyl)cyclopentadienyl tris(n-propylamino)Zirconium(IV)(Zr(F₂HGe-Cp)(NHnPr)₃); (difluorogermyl)cyclopentadienyl tris(Diisopropylamino)Zirconium(IV) (Zr(F₂HGe-Cp)(NiPr₂)₃);(difluorogermyl)cyclopentadienyl tris(isopropylamino)Zirconium(IV)(Zr(F₂HGe-Cp)(NH iPr)₃); (difluorogermyl)cyclopentadienyl tris(Din-butylamino)Zirconium(IV) (Zr(F₂HGe-Cp)(NnBu₂)₃);(difluorogermyl)cyclopentadienyl tris(n-butylamino)Zirconium(IV)(Zr(F₂HGe-Cp)(NHnBu)₃); (difluorogermyl)cyclopentadienyl tris(Diisobutylamino)Zirconium(IV) (Zr(F₂HGe-Cp)(NiBu₂)₃);(difluorogermyl)cyclopentadienyl tris(isobutylamino)Zirconium(IV)(Zr(F₂HGe-Cp)(NHiBu)₃); (difluorogermyl)cyclopentadienyl tris(Disec-butylamino)Zirconium(IV) (Zr(F₂HGe-Cp)(NsBu₂)₃);(difluorogermyl)cyclopentadienyl tris(sec-butylamino)Zirconium(IV)(Zr(F₂HGe-Cp)(NHsBu)₃); (difluorogermyl)cyclopentadienyl tris(Ditert-butylamino)Zirconium(IV) (Zr(F₂HGe-Cp)(NtBu₂)₃);(difluorogermyl)cyclopentadienyl tris(tert-butylamino)Zirconium(IV)(Zr(F₂HGe-Cp)(NHtBu)₃); (monofluorogermyl)cyclopentadienyltris(Dimethylamino)Zirconium(IV) (Zr(FH₂Ge-Cp)(NMe₂)₃);(monofluorogermyl)cyclopentadienyl tris(methylamino)Zirconium(IV)(Zr(FH₂Ge-Cp)(NHMe)₃); (monofluorogermyl)cyclopentadienyltris(Diethylamino)Zirconium(IV) (Zr(FH₂Ge-Cp)(NEt₂)₃);(monofluorogermyl)cyclopentadienyl tris(ethylamino)Zirconium(IV)(Zr(FH₂Ge-Cp)(NHEO₃); (monofluorogermyl)cyclopentadienyltris(Ethylmethylamino)Zirconium(IV) (Zr(FH₂Ge-Cp)(NEtMe)₃);(monofluorogermyl)cyclopentadienyl tris(Di n-propylamino)Zirconium(IV)(Zr(FH₂Ge-Cp)(NnPr₂)₃); (monofluorogermyl)cyclopentadienyltris(n-propylamino)Zirconium(IV) (Zr(FH₂Ge-Cp)(NHnPr)₃);(monofluorogermyl)cyclopentadienyl tris(Diisopropylamino)Zirconium(IV)(Zr(FH₂Ge-Cp)(NiPr₂)₃); (monofluorogermyl)cyclopentadienyltris(isopropylamino)Zirconium(IV) (Zr(FH₂Ge-Cp)(NHiPr)₃);(monofluorogermyl)cyclopentadienyl tris(Di n-butylamino)Zirconium(IV)(Zr(FH₂Ge-Cp)(NnBu₂)₃); (monofluorogermyl)cyclopentadienyltris(n-butylamino)Zirconium(IV) (Zr(FH₂Ge-Cp)(NHnBu)₃);(monofluorogermyl)cyclopentadienyl tris(Di isobutylamino)Zirconium(IV)(Zr(FH₂Ge-Cp)(NiBu₂)₃) (monofluorogermyl)cyclopentadienyltris(isobutylamino)Zirconium(IV) (Zr(FH₂Ge-Cp)(NHiBu)₃);(monofluorogermyl)cyclopentadienyl tris(Di sec-butylamino)Zirconium(IV)(Zr(FH₂Ge-Cp)(NsBu₂)₃); (monofluorogermyl)cyclopentadienyltris(sec-butylamino)Zirconium(IV) (Zr(FH₂Ge-Cp)(NHsBO₃);(monofluorogermyl)cyclopentadienyl tris(Di tert-butylamino)Zirconium(IV)(Zr(FH₂Ge-Cp)(NtBu₂)₃); (monofluorogermyl)cyclopentadienyltris(tert-butylamino)Zirconium(IV) (Zr(FH₂Ge-Cp)(NHtBu)₃); (fluorodimethylgermyl)cyclopentadienyl tris(Dimethylamino) Zirconium(IV)(Zr(FMe₂Ge-Cp)(NMe₂)₃); (fluoro dimethylgermyl)cyclopentadienyltris(methylamino)Zirconium(IV) (Zr(FMe₂Ge-Cp)(NHMe)₃); (fluorodimethylgermyl)cyclopentadienyl tris(Diethylamino)Zirconium(IV)(Zr(FMe₂Ge-Cp)(NEt₂)₃); (fluoro dimethylgermyl)cyclopentadienyltris(ethylamino)Zirconium(IV) (Zr(FMe₂Ge-Cp)(NHEt)₃); (fluorodimethylgermyl)cyclopentadienyl tris(Ethylmethylamino)Zirconium(IV)(Zr(FMe₂Ge-Cp)(NEtMe)₃); (fluoro dimethylgermyl)cyclopentadienyl tris(Din-propylamino) Zirconium(IV) (Zr(FMe₂Ge-Cp)(NnPr₂)₃); (fluorodimethylgermyl)cyclopentadienyl tris(n-propylamino)Zirconium(IV)(Zr(FMe₂Ge-Cp)(NHnPr)₃); (fluoro dimethylgermyl)cyclopentadienyltris(Diisopropylamino)Zirconium(IV) (Zr(FMe₂Ge-Cp)(NiPr₂)₃); (fluorodimethylgermyl)cyclopentadienyl tris(isopropylamino) Zirconium(IV)(Zr(FMe₂Ge-Cp)(NHiPr)₃); (fluoro dimethylgermyl)cyclopentadienyl tris(Din-butylamino)Zirconium(IV) (Zr(FMe₂Ge-Cp)(NnBu₂)₃); (fluorodimethylgermyl)cyclopentadienyl tris(n-butylamino)Zirconium(IV)(Zr(FMe₂Ge-Cp)(NHnBu)₃); (fluoro dimethylgermyl)cyclopentadienyl tris(Diisobutylamino)Zirconium(IV) (Zr(FMe₂Ge-Cp)(NiBu₂)₃); (fluorodimethylgermyl)cyclopentadienyl tris(isobutylamino) Zirconium(IV)(Zr(FMe₂Ge-Cp)(NHiBu)₃); (fluoro dimethylgermyl)cyclopentadienyl tris(Disec-butylamino) Zirconium(IV) (Zr(FMe₂Ge-Cp)(NsBu₂)₃); (fluorodimethylgermyl)cyclopentadienyl tris(sec-butylamino)Zirconium(IV)(Zr(FMe₂Ge-Cp)(NHsBu)₃); (fluoro dimethylgermyl)cyclopentadienyl tris(Ditert-butylamino)Zirconium(IV) (Zr(FMe₂Ge-Cp)(NtBu₂)₃); (fluorodimethylgermyl)cyclopentadienyl tris(tert-butylamino) Zirconium(IV)(Zr(FMe₂Ge-Cp)(NHtBu)₃); (tris(trifluoromethyl)germyl)cyclopentadienyltris(Dimethylamino) Zirconium(IV) (Zr((CF₃)₃Ge-Cp)(NMe₂)₃);(tris(trifluoromethyl)germyl)cyclopentadienyl tris(methylamino)Zirconium(IV) (Zr((CF₃)₃Ge-Cp)(NHMe)₃);(tris(trifluoromethyl)germyl)cyclopentadienyl tris(Diethylamino)Zirconium(IV) (Zr((CF₃)₃Ge-Cp)(NEt₂)₃);(tris(trifluoromethyl)germyl)cyclopentadienyl tris(ethylamino)Zirconium(IV) (Zr((CF₃)₃Ge-Cp)(NHEt)₃);(tris(trifluoromethyl)germyl)cyclopentadienyl tris(Ethylmethylamino)Zirconium(IV) (Zr((CF₃)₃Ge-Cp)(NEtMe)₃);(tris(trifluoromethyl)germyl)cyclopentadienyl tris(Di n-propylamino)Zirconium(IV) (Zr((CF₃)₃Ge-Cp)(NnPr₂)₃);(tris(trifluoromethyl)germyl)cyclopentadienyl tris(n-propylamino)Zirconium(IV) (Zr((CF₃)₃Ge-Cp)(NHnPr)₃);(tris(trifluoromethyl)germyl)cyclopentadienyl tris(Diisopropylamino)Zirconium(IV) (Zr((CF₃)₃Ge-Cp)(NiPr₂)₃);(tris(trifluoromethyl)germyl)cyclopentadienyl tris(isopropylamino)Zirconium(IV) (Zr((CF₃)₃Ge-Cp)(NHiPr)₃);(tris(trifluoromethyl)germyl)cyclopentadienyl tris(Di n-butylamino)Zirconium(IV) (Zr((CF₃)₃Ge-Cp)(NnBu₂)₃);(tris(trifluoromethyl)germyl)cyclopentadienyl tris(n-butylamino)Zirconium(IV) (Zr((CF₃)₃Ge-Cp)(NHnBu)₃);(tris(trifluoromethyl)germyl)cyclopentadienyl tris(Di isobutylamino)Zirconium(IV) (Zr((CF₃)₃Ge-Cp)(NiBu₂)₃);(tris(trifluoromethyl)germyl)cyclopentadienyl tris(isobutylamino)Zirconium(IV) (Zr((CF₃)₃Ge-Cp)(NHiBu)₃);(tris(trifluoromethyl)germyl)cyclopentadienyl tris(Di sec-butylamino)Zirconium(IV) (Zr((CF₃)₃Ge-Cp)(NsBu₂)₃);(tris(trifluoromethyl)germyl)cyclopentadienyl tris(sec-butylamino)Zirconium(IV) (Zr((CF₃)₃Ge-Cp)(NHsBu)₃);(tris(trifluoromethyl)germyl)cyclopentadienyl tris(Di tert-butylamino)Zirconium(IV) (Zr((CF₃)₃Ge-Cp)(NtBu₂)₃);(tris(trifluoromethyl)germyl)cyclopentadienyl tris(tert-butylamino)Zirconium(IV) (Zr((CF₃)₃Ge-Cp)(NHtBu)₃);(bis(trifluoromethyl)germyl)cyclopentadienyl tris(Dimethylamino)Zirconium(IV) (Zr((CF₃)₂HGe-Cp)(NMe₂)₃);(bis(trifluoromethyl)germyl)cyclopentadienyl tris(methylamino)Zirconium(IV) (Zr((CF₃)₂HGe-Cp)(NHMe)₃);(bis(trifluoromethyl)germyl)cyclopentadienyl tris(Diethylamino)Zirconium(IV) (Zr((CF₃)₂HGe-Cp)(NEt₂)₃);(bis(trifluoromethyl)germyl)cyclopentadienyl tris(ethylamino)Zirconium(IV) (Zr((CF₃)₂HGe-Cp)(NHEt)₃);(bis(trifluoromethyl)germyl)cyclopentadienyl tris(Ethylmethylamino)Zirconium(IV) (Zr((CF₃)₂HGe-Cp)(NEtMe)₃);(bis(trifluoromethyl)germyl)cyclopentadienyl tris(Di n-propylamino)Zirconium(IV) (Zr((CF₃)₂HGe-Cp)(NnPr₂)₃);(bis(trifluoromethyl)germyl)cyclopentadienyl tris(n-propylamino)Zirconium(IV) (Zr((CF₃)₂HGe-Cp)(NHnPr)₃);(bis(trifluoromethyl)germyl)cyclopentadienyl tris(Diisopropylamino)Zirconium(IV) (Zr((CF₃)₂HGe-Cp)(NiPr₂)₃);(bis(trifluoromethyl)germyl)cyclopentadienyl tris(isopropylamino)Zirconium(IV) (Zr((CF₃)₂HGe-Cp)(NHiPr)₃);(bis(trifluoromethyl)germyl)cyclopentadienyl tris(Di n-butylamino)Zirconium(IV) (Zr((CF₃)₂HGe-Cp)(NnBu₂)₃);(bis(trifluoromethyl)germyl)cyclopentadienyl tris(n-butylamino)Zirconium(IV) (Zr((CF₃)₂HGe-Cp)(NHnBu)₃);(bis(trifluoromethyl)germyl)cyclopentadienyl tris(Di isobutylamino)Zirconium(IV) (Zr((CF₃)₂HGe-Cp)(NiBu₂)₃);(bis(trifluoromethyl)germyl)cyclopentadienyl tris(isobutylamino)Zirconium(IV) (Zr((CF₃)₂HGe-Cp)(NHiBu)₃);(bis(trifluoromethyl)germyl)cyclopentadienyl tris(Di sec-butylamino)Zirconium(IV) (Zr((CF₃)₂HGe-Cp)(NsBu₂)₃);(bis(trifluoromethyl)germyl)cyclopentadienyl tris(sec-butylamino)Zirconium(IV) (Zr((CF₃)₂HGe-Cp)(NHsBu)₃);(bis(trifluoromethyl)germyl)cyclopentadienyl tris(Di tert-butylamino)Zirconium(IV) (Zr((CF₃)₂HGe-Cp)(NtBu₂)₃);(bis(trifluoromethyl)germyl)cyclopentadienyl tris(tert-butylamino)Zirconium(IV) (Zr((CF₃)₂HGe-Cp)(NHtBu)₃);((trifluoromethyl)dimethylgermyl)cyclopentadienyl tris(Dimethylamino)Zirconium(IV) (Zr((CF₃)Me₂Ge-Cp)(NMe₂)₃);((trifluoromethyl)dimethylgermyl)cyclopentadienyl tris(methylamino)Zirconium(IV) (Zr((CF₃)Me₂Ge-Cp)(NHMe)₃);((trifluoromethyl)dimethylgermyl)cyclopentadienyl tris(Diethylamino)Zirconium(IV) (Zr((CF₃)Me₂Ge-Cp)(NEt₂)₃);((trifluoromethyl)dimethylgermyl)cyclopentadienyl tris(ethylamino)Zirconium(IV) (Zr((CF₃)Me₂Ge-Cp)(NHEt)₃);((trifluoromethyl)dimethylgermyl)cyclopentadienyltris(Ethylmethylamino)Zirconium(IV) (Zr((CF₃)Me₂Ge-Cp)(NEtMe)₃);((trifluoromethyl)dimethylgermyl)cyclopentadienyl tris(Din-propylamino)Zirconium(IV) (Zr((CF₃)Me₂Ge-Cp)(NnPr₂)₃);((trifluoromethyl)dimethylgermyl)cyclopentadienyl tris(n-propylamino)Zirconium(IV) (Zr((CF₃)Me₂Ge-Cp)(NHnPr)₃);((trifluoromethyl)dimethylgermyl)cyclopentadienyl tris(Diisopropylamino)Zirconium(IV) (Zr((CF₃)Me₂Ge-Cp)(NiPr₂)₃);((trifluoromethyl)dimethylgermyl)cyclopentadienyl tris(isopropylamino)Zirconium(IV) (Zr((CF₃)Me₂Ge-Cp)(NHiPr)₃);((trifluoromethyl)dimethylgermyl)cyclopentadienyl tris(Din-butylamino)Zirconium(IV) (Zr((CF₃)Me₂Ge-Cp)(NnBu₂)₃);((trifluoromethyl)dimethylgermyl)cyclopentadienyl tris(n-butylamino)Zirconium(IV) (Zr((CF₃)Me₂Ge-Cp)(NHnBu)₃);((trifluoromethyl)dimethylgermyl)cyclopentadienyl tris(Diisobutylamino)Zirconium(IV) (Zr((CF₃)Me₂Ge-Cp)(NiBu₂)₃);((trifluoromethyl)dimethylgermyl)cyclopentadienyl tris(isobutylamino)Zirconium(IV) (Zr((CF₃)Me₂Ge-Cp)(NHiBu)₃);((trifluoromethyl)dimethylgermyl)cyclopentadienyl tris(Disec-butylamino)Zirconium(IV) (Zr((CF₃)Me₂Ge-Cp)(NsBu₂)₃);((trifluoromethyl)dimethylgermyl)cyclopentadienyl tris(sec-butylamino)Zirconium(IV) (Zr((CF₃)Me₂Ge-Cp)(NHsBu)₃);((trifluoromethyl)dimethylgermyl)cyclopentadienyl tris(Ditert-butylamino)Zirconium(IV) (Zr((CF₃)Me₂Ge-Cp)(NtBu₂)₃); and((trifluoromethyl)dimethylgermyl)cyclopentadienyl tris(tert-butylamino)Zirconium(IV) (Zr((CF₃)Me₂Ge-Cp)(NHtBu)₃).
 15. The process of claim 13,wherein the Germanium- and Zirconium-containing precursor is selectedfrom the group consisting of: (trimethylgermyl)cyclopentadienyltris(methoxy)Zirconium(IV) (Zr(TMG-Cp)(OMe)₃);(trimethylgermyl)cyclopentadienyl tris(ethoxy)Zirconium(IV)(Zr(TMG-Cp)(OEt)₃); (trimethylgermyl)cyclopentadienyl tris(n-propoxy)Zirconium(IV) (Zr(TMG-Cp)(OnPr)₃); (trimethylgermyl)cyclopentadienyltris(isopropoxy)Zirconium(IV) (Zr(TMG-Cp)(OiPr)₃);(trimethylgermyl)cyclopentadienyl tris(tert-butoxy)Zirconium(IV)(Zr(TMG-Cp)(OtBu)₃); (trimethylgermyl)cyclopentadienyl tris(sec-butoxy)Zirconium(IV) (Zr(TMG-Cp)(OsBu)₃); (trimethylgermyl)cyclopentadienyltris(n-butoxy)Zirconium(IV) (Zr(TMG-Cp)(OnBu)₃);(trimethylgermyl)cyclopentadienyl tris(iso-butoxy)Zirconium(IV)(Zr(TMG-Cp)(OiBu)₃); (dimethylgermyl)cyclopentadienyltris(methoxy)Zirconium(IV) (Zr(DMG-Cp)(OMe)₃);(dimethylgermyl)cyclopentadienyl tris(ethoxy) Zirconium(IV)(Zr(DMG-Cp)(OEt)₃); (dimethylgermyl)cyclopentadienyltris(n-propoxy)Zirconium(IV) (Zr(DMG-Cp)(OnPr)₃);(dimethylgermyl)cyclopentadienyl tris(isopropoxy)Zirconium(IV)(Zr(DMG-Cp)(OiPr)₃); (dimethylgermyl)cyclopentadienyl tris(tert-butoxy)Zirconium(IV) (Zr(DM G-Cp)(OtBu)₃); (dimethylgermyl)cyclopentadienyltris(sec-butoxy)Zirconium(IV) (Zr(DMG-Cp)(OsBu)₃);(dimethylgermyl)cyclopentadienyl tris(n-butoxy)Zirconium(IV)(Zr(DMG-Cp)(OnBu)₃); (dimethylgermyl)cyclopentadienyl tris(isobutoxy)Zirconium(IV) (Zr(DM G-Cp)(OiBu)₃); (trifluorogermyl)cyclopentadienyltris(methoxy)Zirconium(IV) (Zr(F₃Ge-Cp)(OMe)₃);(trifluorogermyl)cyclopentadienyl tris(ethoxy)Zirconium(IV)(Zr(F₃Ge-Cp)(OEt)₃); (trifluorogermyl)cyclopentadienyltris(n-propoxy)Zirconium(IV) (Zr(F₃Ge-Cp)(OnPr)₃);(trifluorogermyl)cyclopentadienyl tris(isopropoxy) Zirconium(IV)(Zr(F₃Ge-Cp)(OiPr)₃); (trifluorogermyl)cyclopentadienyltris(tert-butoxy)Zirconium(IV) (Zr(F₃Ge-Cp)(OtBu)₃);(trifluorogermyl)cyclopentadienyl tris(sec-butoxy)Zirconium(IV)(Zr(F₃Ge-Cp)(OsBu)₃); (trifluorogermyl)cyclopentadienyltris(n-butoxy)Zirconium(IV) (Zr(F₃Ge-Cp)(OnBu)₃);(trifluorogermyl)cyclopentadienyl tris(isobutoxy) Zirconium(IV)(Zr(F₃Ge-Cp)(OiBu)₃); (difluorogermyl)cyclopentadienyltris(methoxy)Zirconium(IV) (Zr(F₂HGe-Cp)(OMe)₃);(difluorogermyl)cyclopentadienyl tris(ethoxy)Zirconium(IV)(Zr(F₂HGe-Cp)(OEt)₃); (difluorogermyl)cyclopentadienyltris(n-propoxy)Zirconium(IV) (Zr(F₂HGe-Cp)(OnPr)₃);(difluorogermyl)cyclopentadienyl tris(isopropoxy) Zirconium(IV)(Zr(F₂HGe-Cp)(OiPr)₃); (difluorogermyl)cyclopentadienyltris(tert-butoxy)Zirconium(IV) (Zr(F₂HGe-Cp)(OtBu)₃);(difluorogermyl)cyclopentadienyl tris(sec-butoxy)Zirconium(IV)(Zr(F₂HGe-Cp)(OsBu)₃); (difluorogermyl)cyclopentadienyltris(n-butoxy)Zirconium(IV) (Zr(F₂HGe-Cp)(OnBu)₃);(difluorogermyl)cyclopentadienyl tris(isobutoxy)Zirconium(IV)(Zr(F₂HGe-Cp)(OiBu)₃); (monofluorogermyl)cyclopentadienyltris(methoxy)Zirconium(IV) (Zr(FH₂Ge-Cp)(OMe)₃);(monofluorogermyl)cyclopentadienyl tris(ethoxy)Zirconium(IV)(Zr(FH₂Ge-Cp)(OEt)₃); (monofluorogermyl)cyclopentadienyltris(n-propoxy)Zirconium(IV) (Zr(FH₂Ge-Cp)(OnPr)₃);(monofluorogermyl)cyclopentadienyl tris(isopropoxy)Zirconium(IV)(Zr(FH₂Ge-Cp)(OiPr)₃); (monofluorogermyl)cyclopentadienyltris(tert-butoxy)Zirconium(IV) (Zr(FH₂Ge-Cp)(OtBu)₃);(monofluorogermyl)cyclopentadienyl tris(sec-butoxy)Zirconium(IV)(Zr(FH₂Ge-Cp)(OsBu)₃); (monofluorogermyl)cyclopentadienyltris(n-butoxy)Zirconium(IV) (Zr(FH₂Ge-Cp)(OnBu)₃);(monofluorogermyl)cyclopentadienyl tris(isobutoxy)Zirconium(IV)(Zr(FH₂Ge-Cp)(OiBu)₃); (fluoro dimethylgermyl)cyclopentadienyltris(methoxy)Zirconium(IV) (Zr(FMe₂Ge-Cp)(OMe)₃); (fluorodimethylgermyl)cyclopentadienyl tris(ethoxy)Zirconium(IV)(Zr(FMe₂Ge-Cp)(OEt)₃); (fluoro dimethylgermyl)cyclopentadienyltris(n-propoxy)Zirconium(IV) (Zr(FMe₂Ge-Cp)(OnPr)₃); (fluorodimethylgermyl)cyclopentadienyl tris(isopropoxy)Zirconium(IV)(Zr(FMe₂Ge-Cp)(OiPr)₃); (fluoro dimethylgermyl)cyclopentadienyltris(tert-butoxy)Zirconium(IV) (Zr(FMe₂Ge-Cp)(OtBu)₃); (fluorodimethylgermyl)cyclopentadienyl tris(sec-butoxy)Zirconium(IV)(Zr(FMe₂Ge-Cp)(OsBu)₃); (fluoro dimethylgermyl)cyclopentadienyltris(n-butoxy)Zirconium(IV) (Zr(FMe₂Ge-Cp)(OnBu)₃); (fluorodimethylgermyl)cyclopentadienyl tris(isobutoxy)Zirconium(IV)(Zr(FMe₂Ge-Cp)(OiBu)₃); (tris(trifluoromethyl)germyl)cyclopentadienyltris(methoxy) Zirconium(IV) (Zr((CF₃)₃Ge-Cp)(OMe)₃);(tris(trifluoromethyl)germyl)cyclopentadienyl tris(ethoxy)Zirconium(IV)(Zr((CF₃)₃Ge-Cp)(OEt)₃); (tris(trifluoromethyl)germyl)cyclopentadienyltris(n-propoxy) Zirconium(IV) (Zr((CF₃)₃Ge-Cp)(OnPr)₃);(tris(trifluoromethyl)germyl)cyclopentadienyl tris(isopropoxy)Zirconium(IV) (Zr((CF₃)₃Ge-Cp)(OiPr)₃);(tris(trifluoromethyl)germyl)cyclopentadienyl tris(tert-butoxy)Zirconium(IV) (Zr((CF₃)₃Ge-Cp)(OtBu)₃);(tris(trifluoromethyl)germyl)cyclopentadienyl tris(sec-butoxy)Zirconium(IV) (Zr((CF₃)₃Ge-Cp)(OsBu)₃);(tris(trifluoromethyl)germyl)cyclopentadienyl tris(n-butoxy)Zirconium(IV) (Zr((CF₃)₃Ge-Cp)(OnBu)₃);(tris(trifluoromethyl)germyl)cyclopentadienyl tris(isobutoxy)Zirconium(IV) (Zr((CF₃)₃Ge-Cp)(OiBu)₃);(bis(trifluoromethyl)germyl)cyclopentadienyl tris(methoxy) Zirconium(IV)(Zr((CF₃)₂HGe-Cp)(OMe)₃); (bis(trifluoromethyl)germyl)cyclopentadienyltris(ethoxy)Zirconium(IV) (Zr((CF₃)₂HGe-Cp)(OEt)₃);(bis(trifluoromethyl)germyl)cyclopentadienyl tris(n-propoxy)Zirconium(IV) (Zr((CF₃)₂HGe-Cp)(OnPr)₃);(bis(trifluoromethyl)germyl)cyclopentadienyl tris(isopropoxy)Zirconium(IV) (Zr((CF₃)₂HGe-Cp)(OiPr)₃);(bis(trifluoromethyl)germyl)cyclopentadienyl tris(tert-butoxy)Zirconium(IV) (Zr((CF₃)₂HGe-Cp)(OtBu)₃);(bis(trifluoromethyl)germyl)cyclopentadienyl tris(sec-butoxy)Zirconium(IV) (Zr((CF₃)₂HGe-Cp)(OsBu)₃);(bis(trifluoromethyl)germyl)cyclopentadienyl tris(n-butoxy)Zirconium(IV) (Zr((CF₃)₂HGe-Cp)(OnBu)₃);(bis(trifluoromethyl)germyl)cyclopentadienyl tris(iso-butoxy)Zirconium(IV) (Zr((CF₃)₂HGe-Cp)(OiBu)₃);((trifluoromethyl)dimethylgermyl)cyclopentadienyl tris(methoxy)Zirconium(IV) (Zr((CF₃)Me₂Ge-Cp)(OMe)₃);((trifluoromethyl)dimethylgermyl)cyclopentadienyl tris(ethoxy)Zirconium(IV) (Zr((CF₃)Me₂Ge-Cp)(OEt)₃);((trifluoromethyl)dimethylgermyl)cyclopentadienyl tris(n-propoxy)Zirconium(IV) (Zr((CF₃)Me₂Ge-Cp)(OnPr)₃);((trifluoromethyl)dimethylgermyl)cyclopentadienyl tris(isopropoxy)Zirconium(IV) (Zr((CF₃)Me₂Ge-Cp)(OiPr)₃);((trifluoromethyl)dimethylgermyl)cyclopentadienyl tris(tert-butoxy)Zirconium(IV) (Zr((CF₃)Me₂Ge-Cp)(OtBu)₃);((trifluoromethyl)dimethylgermyl)cyclopentadienyl tris(sec-butoxy)Zirconium(IV) (Zr((CF₃)Me₂Ge-Cp)(OsBu)₃);((trifluoromethyl)dimethylgermyl)cyclopentadienyl tris(n-butoxy)Zirconium(IV) (Zr((CF₃)Me₂Ge-Cp)(OnBu)₃); and((trifluoromethyl)dimethylgermyl)cyclopentadienyl tris(isobutoxy)Zirconium(IV) (Zr((CF₃)Me₂Ge-Cp)(OiBu)₃).
 16. The process of claim 13,further comprising introducing at least one reactant into the reactor.17. The process of claim 16, wherein the reactant is selected from thegroup consisting of H₂, H₂CO N₂H₄, NH₃, SiH₄, Si₂H₆, Si₃H₈, SiH₂Me₂,SiH₂Et₂, N(SiH₃)₃, hydrogen radicals thereof, and mixtures thereof. 18.The process of claim 16, wherein the reactant is selected from the groupconsisting of: O₂, O₃, H₂O, H₂O₂ NO, N₂O, NO₂, oxygen radicals thereof,and mixtures thereof.
 19. The process of claim 16, wherein theGermanium- and Zirconium-containing precursor and the reactant areintroduced into the reactor simultaneously and the reactor is configuredfor chemical vapor deposition.
 20. The process of claim 16, wherein theGermanium- and Zirconium-containing precursor and the reactant areintroduced into the chamber sequentially and the reactor is configuredfor atomic layer deposition.